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  • Articles  (14,370)
  • Wiley  (14,370)
  • Water Resources Research  (4,823)
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  • 1
    Publication Date: 2015-08-08
    Description: We investigate how the choice of injection mode impacts transport properties in kilometer-scale three-dimensional discrete fracture networks (DFN). The choice of injection mode, resident or flux-weighted, is designed to mimic different physical phenomena. It has been hypothesized that solute plumes injected under resident conditions evolve to behave similarly to solutes injected under flux-weighted conditions. Previously, computational limitations have prohibited the large scale simulations required to investigate this hypothesis. We investigate this hypothesis by using a high performance DFN suite, dfnWorks , to simulate flow in kilometer-scale three-dimensional DFNs based on fractured granite at the Forsmark site in Sweden, and adopt a Lagrangian approach to simulate transport therein. Results show that after traveling through a pre-equilibrium region both injection methods exhibit linear scaling of the first moment of travel time and power law scaling of the breakthrough curve with similar exponents, slightly larger than two. The physical mechanisms behind this evolution appear to be the combination of in-network channeling of mass into larger fractures, which offer reduced resistance to flow, and in-fracture channeling, which results from the topology of the DFN. This article is protected by copyright. All rights reserved.
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  • 2
    Publication Date: 2015-08-08
    Description: Hydrologic ensemble forecasts driven by atmospheric ensemble prediction systems need statistical post-processing in order to account for systematic errors in terms of both location and spread. Runoff is an inherently multivariate process with typical events lasting from hours in case of floods to weeks or even months in case of droughts. This calls for multivariate post-processing techniques that yield well calibrated forecasts in univariate terms and ensure a realistic temporal dependence structure at the same time. To this end, the univariate ensemble model output statistics (EMOS) post-processing method is combined with two different copula approaches that ensure multivariate calibration throughout the entire forecast horizon. The domain of this study covers three sub-catchments of the river Rhine that represent different sizes and hydrological regimes: the Upper Rhine up to the gauge Maxau, the river Moselle up to the gauge Trier, and the river Lahn up to the gauge Kalkofen. In this study the two approaches to model the temporal dependence structure are ensemble copula coupling (ECC), which preserves the dependence structure of the raw ensemble, and a Gaussian copula approach (GCA), which estimates the temporal correlations from training observations. The results indicate that both methods are suitable for modelling the temporal dependencies of probabilistic hydrologic forecasts. This article is protected by copyright. All rights reserved.
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  • 3
    Publication Date: 2015-08-08
    Description: A three-dimensional mathematical model that describes transport of contaminant in a horizontal aquifer with simultaneous diffusion into a fractured clay formation is proposed. A group of semi-analytical solutions is derived based on specific initial and boundary conditions as well as various source functions. The analytical model solutions are evaluated by numerical Laplace inverse transformation and analytical Fourier inverse transformation. The model solutions can be used to study the fate and transport in a three-dimensional spatial domain in which a non-aqueous phase liquid exists as a pool atop a fractured low permeability clay layer. The non-aqueous phase liquid gradually dissolves into the groundwater flowing past the pool, while simultaneously diffusing into the fractured clay formation below the aquifer. Mass transfer of the contaminant into the clay formation is demonstrated to be significantly enhanced by the existence of the fractures, even though the volume of fractures is relatively small compared to the volume of the clay matrix. The model solution is a useful tool in assessing contaminant attenuation processes in a confined aquifer underlain by a fractured clay formation. This article is protected by copyright. All rights reserved.
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  • 4
    Publication Date: 2015-08-04
    Description: The search for novel chemical architectures displaying improved biological properties is a never-ending synthetic challenge. In this context many new test structures are often conceived by selecting and replicating specific design elements from naturally occurring molecules and displaying them in an alternative format by way of a new chemical assembly. Constructing these newly designed compounds can be a timely and expensive process especially when a large quantity of the target material is required for physiochemical and property testing. To permit easier scale up and safer working practice many chemical researchers are employing flow chemistry approaches to aid in their synthesis challenges. Herein we report on the preparation of a key spirocyclic lactone using flow based reaction processing techniques.
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  • 5
    Publication Date: 2015-07-29
    Description: This work focuses on the implementation of a Shallow Water-Exner model for compound natural channels with complex geometry and movable bed within the finite volume framework. The model is devised for compound channels modeling: cross-section overbanks are treated with fixed bed conditions, while the main channel is left free to modify its morphology. A capacitive approach is used for bedload transport modeling, in which the solid flow rates are estimated with bedload transport formulas. The model equations pose some numerical issues in the case of natural channels, where bedload transport may occur for both subcritical and supercritical flows and geometry varies in space. An explicit path-conservative scheme, designed to overcome all these issues, is presented in the paper. The scheme solves liquid and solid phases dynamics in a coupled manner, in order to correctly model near critical currents/channel interactions and is well-balanced, that is able to properly reproduce steady states. The Roe and Osher Riemann solvers are implemented, so as to take into account the spatial geometry variations of natural channels. The scheme reaches up to 2 nd order accuracy. Validation is performed with fixed and movable bed test cases whose analytical solution is known, and with flume experimental data. An application of the model to a real case study is also shown. This article is protected by copyright. All rights reserved.
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  • 6
    Publication Date: 2015-08-05
    Description: In this paper we use a physical modelling approach to explore the effect of lateral confinement on gravel bed river planform style, bed morphology, and sediment transport processes. A set of 27 runs was performed in a large flume (25 m long, 2.9 m wide), with constant longitudinal slope (0.01) and uniform grain size (1 mm), changing the water discharge (1.5 to 2.5 l/s) and the channel width (0.15 m to 1.5 m) to model a wide range of channel configurations, from narrow, straight, embanked channels to wide braided networks. The outcomes of each run were characterized by a detailed digital elevation model describing channel morphology, a map of dry areas and areas actively transporting sediment within the channel, and continuous monitoring of the amount of sediment transported through the flume outlet. Analysis reveals strong relationships between unit stream power and parameters describing the channel morphology. In particular, a smooth transition is observed between narrow channels with an almost rectangular cross section profile (with sediment transport occurring across the entire channel width) and complex braided networks where only a limited proportion (30%) of the bed is active. This transition is captured by descriptors of the bed elevation frequency distribution, e.g. standard deviation, skewness and kurtosis. These summary statistics represent potentially useful indicators of bed morphology that are compared with other commonly used summary indicators such as the braiding index and the type and number of bars. This article is protected by copyright. All rights reserved.
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  • 7
    Publication Date: 2015-08-08
    Description: Mass transfer from single CO 2 Taylor bubbles in vertical mini channels was measured for channel hydraulic diameters, D h , from 5.5 to 8.0 mm. The effects of channel geometries on the mass transfer were also investigated by using square ducts and circular pipes. Bubble rising velocities, v B , in the ducts were much faster than those in the pipes due to large liquid flow areas in the corners of the ducts. The values of mass transfer coefficients, k L , in the pipes were almost the same as those in the ducts, in spite of a large difference in v B . Sherwood numbers, Sh D , using D h as a characteristic length are well correlated in terms of the Eötvös number. The proposed Sh D correlation can well predict a long-term dissolution process of a Taylor bubble.
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  • 8
    Publication Date: 2015-08-19
    Description: The phase-field method coupled with the Navier-Stokes equations is a rather new approach for scale-resolving numerical simulation of interfacial two-phase flows. The intention is to implement it as finite-volume method in the open source library for computational continuum mechanics OpenFOAM® and make it freely available. An overview on the governing equations is given and the numerical method is shortly discussed. The focus is on application and validation of the code for some fundamental wetting phenomena, namely the capillary rise in a narrow channel and the spreading of a droplet on a flat surface, which is chemically homogeneous or regularly patterned. The numerical results on static meshes agree well with analytical solutions and experimental/numerical results from literature. Also, first 3D finite-volume simulations with adaptive mesh refinement near the interface are presented as a key element to achieve CPU-time efficient simulations. A phase-field method for interface resolving numerical simulations of two-phase flows is presented and implemented in OpenFOAM®. The method is validated for several capillary flows with moving contact lines and is used to study dynamic droplet spreading on a flat surface by three-dimensional simulations with adaptive mesh refinement near the interface.
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  • 9
    Publication Date: 2015-08-19
    Description: We believe that there are too many models in hydrology and we should ask ourselves the question, if we are currently wasting time and effort in developing another model again instead of focusing on the development of a community hydrological model. In other fields this kind of models have been quite successful, but due to several reasons, no single community model has been developed in the field of hydrology yet. The concept, strength and weakness of a community model was discussed at the Chapman Conference on Catchment Spatial Behaviour and Complex Organisation held in Luxembourg in September 2014. This discussion as well as out own opinions about the potential of a community models, or at least the necessary discussion to establish one are debated in this commentary. This article is protected by copyright. All rights reserved.
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  • 10
    Publication Date: 2015-08-21
    Description: Soil surface sealing is a widespread natural process occurring frequently in bare soil areas between vegetation patches. The low hydraulic conductivity that characterizes the seal layer reduces both infiltration and evaporation fluxes from the soil, and thus has the potential to affect local vegetation water uptake (VWU). This effect is investigated here using experimental data, 2D physically based modelling and a long-term climatic dataset from three dry sites presenting a climatic gradient in the Negev Desert, Israel. The Feddes VWU parameters for the dominant shrub at the study site ( Sarcopoterium spinosum ) were acquired using lysimeter experiments. The results indicate that during the season surface sealing could either increase or decrease VWU depending on initial soil water content, rainfall intensity, and the duration of the subsequent drying intervals. These factors have a marked effect on inter-annual variability of the seal layer effect on VWU, which on average was found to be 26% higher under sealed conditions than in the case of unsealed soil surfaces. The seal layer was found to reduce the period where the vegetation was under water stress by 31% compared with unsealed conditions. This effect was more pronounced for seasons with total rainfall depth higher than 10 cm/y, and was affected by interseasonal climatic variability. These results shed light on the importance of surface sealing in dry environments and its contribution to the resilience of woody vegetation. This article is protected by copyright. All rights reserved.
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  • 11
    Publication Date: 2015-08-23
    Description: Female salmonids bury and lay their eggs in streambeds by digging a pit, which is then covered with sediment from a second pit. The spawning process alters streambed topography, winnows fine sediment, and mixes sediment in the active layer. The resulting egg nests (redds) contain coarser and looser sediments than those of unspawned streambed areas, and display a dune-like shape with an amplitude and length that vary with fish size, substrate conditions, and flow conditions. Redds increase local bed surface roughness (〈10 −1 channel width, W ), but may reduce the size of macro-bedforms by eroding reach scale topography (10 ° -10 1 W ). Research has suggested that spawning may increase flow resistance due to redd form drag, resulting in lower grain shear stress and less particle mobility. Spawning however also prevents streambed armoring through surface and subsurface material mixing, potentially increasing particle mobility. Here, we use 2-dimensional hydraulic modeling with detailed pre- and post-spawning bathymetries and field observations to test the effect of small spawning salmonids on sediment transport. Our results show that topographical roughness added by small-bodied salmon redds has negligible effects on shear stress at the reach-unit scale, and limited effects at the local scale. Conversely, our results indicate sediment mixing reduces armoring and enhances sediment mobility, which increases potential bed load transport by subsequent floods. River restoration in fish-bearing streams should take into consideration the effects of redd excavation on channel stability. This is particularly important for streams that historically supported salmonids, and at present are the focus of habitat restoration actions. This article is protected by copyright. All rights reserved.
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  • 12
    Publication Date: 2015-08-19
    Description: Floods are a natural hazard that affect communities worldwide, but to date the vast majority of flood hazard research and mapping has been undertaken by wealthy developed nations. As populations and economies have grown across the developing world, so too has demand from governments, businesses and NGOs for modelled flood hazard data in these data-scarce regions. We identify six key challenges faced when developing a flood hazard model that can be applied globally, and present a framework methodology that leverages recent cross-disciplinary advances to tackle each challenge. The model produces return period flood hazard maps at ∼90 m resolution for the whole terrestrial land surface between 56˚S and 60˚N, and results are validated against high resolution government flood hazard datasets from the UK and Canada. The global model is shown to capture between two thirds and three quarters of the area determined to be at risk in the benchmark data without generating excessive false positive predictions. When aggregated to ∼1 km, mean absolute error in flooded fraction falls to ∼5%. The full complexity global model contains an automatically parameterised subgrid channel network, and comparison to both a simplified 2D only variant and an independently developed pan-European model shows the explicit inclusion of channels to be a critical contributor to improved model performance. Whilst careful processing of existing global terrain datasets enables reasonable model performance in urban areas, adoption of forthcoming next-generation global terrain datasets will offer the best prospect for a step-change improvement in model performance. This article is protected by copyright. All rights reserved.
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  • 13
    Publication Date: 2015-08-23
    Description: Understanding how channel bed morphology affects flow conditions (and vice versa) is important for a wide range of fluvial processes and practical applications. We investigated interactions between bed roughness and flow velocity in a steep, glacier-fed mountain stream (Riedbach, Ct. Valais, Switzerland) with almost flume-like boundary conditions. Bed gradient increases along the 1-km study reach by roughly one order of magnitude ( S =3-41%), with a corresponding increase in streambed roughness, while flow discharge and width remain approximately constant due to the glacial runoff regime. Streambed roughness was characterized by semi-variograms and standard deviations of point clouds derived from terrestrial laser scanning. Reach-averaged flow velocity was derived from dye tracer breakthrough curves measured by 10 fluorometers installed along the channel. Commonly used flow resistance approaches (Darcy-Weisbach equation and dimensionless hydraulic geometry) were used to relate the measured bulk velocity to bed characteristics. As a roughness measure, D 84 yielded comparable results to more laborious measures derived from point clouds. Flow resistance behavior across this large range of steep slopes agreed with patterns established in previous studies for both lower-gradient and steep reaches, regardless of which roughness measures were used. We linked empirical critical shear stress approaches to the variable power equation for flow resistance to investigate the change of bed roughness with channel slope. The predicted increase in D 84 with increasing channel slope was in good agreement with field observations. This article is protected by copyright. All rights reserved.
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  • 14
    Publication Date: 2015-08-23
    Description: Large wood governs channel morphology, as well as the availability of in-stream habitat, in many forested streams. In this paper we use a stochastic, physically based model to simulate wood recruitment and in-stream geomorphic processes, in order to explore the influence of disturbance history on the availability of aquatic habitat. Specifically, we consider the effects of fire on a range of stream sizes by varying the rate of tree toppling over time in a simulated forest characterized by a tree height of 30 m. We also consider the effects of forest harvesting with various riparian buffer sizes, by limiting the lateral extent of the riparian stand. Our results show that pulsed inputs of wood increase the availability and variability of physical habitat in the post-fire period; reach-averaged pool area and deposit area double in small streams, while side-channels increase by over 50% in intermediate-sized channels. By contrast, forest harvesting reduces the availability of habitat within the reach, though the effects diminish with increasing buffer size or stream width; in laterally stable streams the effects are minimal so long as buffer width is large enough for key pieces to be recruited to the reach. This research emphasizes the importance of natural disturbance in creating and maintaining habitat heterogeneity and shows that scenario-based numerical modeling provides a useful tool for assessing the historical range of variability associated with natural disturbance, as well as changes in habitat relevant to fish. It can be also used to inform forest harvesting and management. This article is protected by copyright. All rights reserved.
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  • 15
    Publication Date: 2015-08-23
    Description: Spreading of conservative solutes in groundwater due to aquifer heterogeneity is quantified by the macrodispersivity, which was found to be scale dependent. It increases with travel distance, stabilizing eventually at a constant value. However, the question of its asymptotic behaviour at very large scale is still a matter of debate. It was surmised in the literature that macrodispersivity scales up following a unique scaling law. Attempts to define such a law were made by fitting a regression line in the log-log representation of an ensemble of macrodispersivities from multiple experiments. The functional relationships differ among the authors, based on the choice of data. Our study revisits the data basis, used for inferring unique scaling, through a detailed analysis of literature marcodispersivities. In addition, values were collected from the most recent tracer tests reported in the literature. We specified a system of criteria for reliability and re-evaluated the reliability of the reported values. The final collection of reliable estimates of macrodispersivity does not support a unique scaling law relationship. On the contrary, our results indicate, that the field data can be explained as a collection of macrodispersivities of aquifers with varying degree of heterogeneity where each exhibits its own constant asymptotic value. Our investigation concludes that transport, and particularly the macrodispersivity, is formation-specific, and that modeling of transport cannot be relegated to a unique scaling law. Instead, transport requires characterization of aquifer properties, e.g. spatial distribution of hydraulic conductivity, and the use of adequate models. This article is protected by copyright. All rights reserved.
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  • 16
    Publication Date: 2015-08-23
    Description: For the past few decades, heat has been used to estimate river-aquifer exchange flux at discrete locations by comparison of river and groundwater temperature. In recent years, heat has also been employed to estimate reach-scale river-aquifer exchange flux based only on river temperature. However, there are many more parameters that govern heat exchange and transport in surface water than in groundwater. In this study, we analyzed the sensitivities of surface water temperature to various parameters and assessed the accuracy of temperature-based estimates of exchange flux in two synthetic rivers and in a field setting. For the large synthetic river with a flow rate of 63 m 3 s −1 (i.e., 5.44 × 10 6 m 3 d −1 ), the upper and lower bounds of the groundwater inflow rate can be determined when the actual groundwater inflow is around 100 m 2 d −1 . For higher and lower fluxes, only minimum and maximum bounds respectively can be determined. For the small synthetic river with the flow rate of 0.63 m 3 s −1 (i.e., 5.44 × 10 4 m 3 d −1 ), the bounds of the groundwater inflow rate can only be estimated when the actual groundwater inflow rate is near 10 m 2 d −1 . In the field setting, results show that the inflow rate must be less than 100 m 2 d −1 , but a lower bound for groundwater inflow cannot be determined. The large ranges of estimated groundwater inflow rates in both theoretical and field settings indicate the need to reduce parameter errors and combine heat measurements with other isotopic and/or chemical methods. This article is protected by copyright. All rights reserved.
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  • 17
    Publication Date: 2015-08-23
    Description: Climate state can be an important predictor of future hydrologic conditions. In ensemble streamflow forecasting, where historical weather inputs or streamflow observations are used to generate the ensemble, climate index weighting is one way to represent the influence of climate state. Using a climate index, each forecast variable member of the ensemble is selectively weighted to reflect the climate state at the time of the forecast. A new approach to climate index weighting of ensemble forecasts is presented. The method is based on a sampling-resampling approach for Bayesian updating. The original hydrologic ensemble members define a sample drawn from the prior distribution; the relationship between the climate index and the ensemble member forecast variable is used to estimate a likelihood function. Given an observation of the climate index at the time of the forecast, the estimated likelihood function is then used to assign weights to each ensemble member. The weights define the probability of each ensemble member outcome given the observed climate index. The weighted ensemble forecast is then used to estimate the posterior distribution of the forecast variable conditioned on the climate index. The Bayesian climate index weighting approach is easy to apply to hydrologic ensemble forecasts; its parameters do not require calibration with hindcasts, and it adapts to the strength of the relation between climate and the forecast variable, defaulting to equal weighting of ensemble members when no relationship exists. A hydrologic forecasting application illustrates the approach and contrasts it with traditional climate index weighting approaches. This article is protected by copyright. All rights reserved.
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  • 18
    Publication Date: 2015-08-15
    Description: Field hydrology is on the decline. Meanwhile, the need for new field-derived insight into the age, origin and pathway of water in the headwaters, where most runoff is generated, is more needed than ever. Water Resources Research (WRR) has included some of the most influential papers in field-based runoff process understanding, particularly in the formative years when the knowledge base was developing rapidly. Here, we take advantage of this 50 th anniversary of the journal to highlight a few of these important field-based papers and show how field scientists have posed strong and sometimes outrageous hypotheses—approaches so needed in an era of largely model-only research. We chronicle the decline in field work and note that it is not only the quantity of field work that is diminishing but its character is changing too: from discovery science to data collection for model parameterisation. While the latter is a necessary activity, the loss of the former is a major concern if we are to advance the science of watershed hydrology. We outline a vision for field research to seek new fundamental understanding, new mechanistic explanations of how watershed systems work, particularly outside the regions of traditional focus. This article is protected by copyright. All rights reserved.
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  • 19
    Publication Date: 2015-08-04
    Description: The influence of water on the catalysis of biphasic Heck alkynylation, a family of palladium-catalyzed carbon-carbon bond formations, was investigated. Kinetic theory derived from Hatta moduli and pseudo-stationary-state approximations discovered that water, in coordination, reductive elimination, and product dissociation reaction steps of the deprotonation catalytic cycle, increases Gibbs energy barriers compared to values previously estimated by density functional theory calculations of purely organic syntheses involving an aryl iodide. On the contrary, water reduces the energy barrier of reductive elimination in the carbopalladation catalytic cycle. Quantum tunneling in proton transfer mechanism might account for the change. Water also influenced the rate-determining steps of the catalytic cycles, and its existence potentially switches the cross-coupling’s mechanism from deprotonation, previously thought to govern the reaction, to carbopalladation. Carbopalladation theory identified the ~35% of the Pd wasted during synthesis was ~10% greater than the amount predicted by deprotonation. Our discoveries enabled E-factor predictions that could someday help reduce chemical wastes generated during materials, natural products, and pharmaceutical manufactures. Theoretical groundwork is laid that enables data-driven research in the academic laboratory and data-driven development by the process chemist.
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  • 20
    Publication Date: 2015-08-04
    Description: A continuous process to produce carbon supported platinum catalysts by polyol reduction was examined. The reactant dispersion was rapidly heated up to reaction temperature while flowing through a directly electrically heated tube followed by a downstream isothermic tubular reactor. Appropriate inner diameters corresponding to desired short heating-up times were calculated. A certain lower limit for the inner diameter is caused by temporary pluggings of particle agglomerates circumventing steady-state operation. Tube diameters were evaluated with respect to heating-up times and plugging. It was proved that with a tubular reactor a continuous preparation of carbon nanotube supported platinum catalysts with a low particle size and evenly distributed particles is possible.
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  • 21
    Publication Date: 2015-08-08
    Description: This work focussed on the mathematical modeling of the separation process in counter-current decanter centrifuges, taking the influence of the sediment build-up and the flow pattern into account. Thus far, separation processes in centrifuges are calculated by means of simplified empirical models based on the so-called sigma-theory. To reduce experimental effort, we have developed a new model, which describes the separation process by considering material functions for sedimentation and the gel point. In addition to that, an arising sediment build-up and a change in the flow conditions are taken into account. The conducted numerical simulations are validated by experiments. Simplified models such as the sigma theory usually depend on experimental data of industrial machines. Our approach shows an enhanced accuracy while not depending on such information. The proposed simulation procedure is adaptable to other types of decanter centrifuges such as co-current machines.
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  • 22
    Publication Date: 2015-08-08
    Description: Catalyzed reaction of sulfite with oxygen is often used by industry for corrosion protection by chemical deoxygenation. The same reaction system is considered very important as a part of atmospheric chemistry due to SO2 immission modeling. In these applications, reaction kinetic data are of crucial importance. In deoxygenation, low concentrations of sulfite close to the stoichiometric ratio to oxygen are being used. Unfortunately, the values of kinetic constants for the reaction are sparse.The reaction kinetics was investigated in a rapid-mixing apparatus, where air or pure oxygen saturated solution containing the catalyst was mixed with aqueous sulfite solution. Mixing ratios with stoichiometric excess of dissolved oxygen were tested.Analysis of literature data suggests that the reaction is of 1.5 order in sulfite, 0 order in oxygen and 0.5 order in cobalt(II) catalyst. These reaction orders had been confirmed in the concentration range tested. The apparent kinetic constant and activation energy are also presented. Crucial importance of proper mixing of the two reacting solutions is reported, which was revealed during the development of the precise experimental technique providing reliable kinetic data.
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  • 23
    Publication Date: 2015-06-04
    Description: We present a novel inverse modeling strategy to estimate spatially distributed parameters of nonlinear models. The maximum a posteriori (MAP) estimators of these parameters are based on a likelihood functional, which contains spatially discrete measurements of the system parameters and spatio-temporally discrete measurements of the transient system states. The piecewise continuity prior for the parameters is expressed via Total Variation (TV) regularization. The MAP estimator is computed by minimizing a non-quadratic objective equipped with the TV operator. We apply this inversion algorithm to estimate hydraulic conductivity of a synthetic confined aquifer from measurements of conductivity and hydraulic head. The synthetic conductivity field is composed of a low-conductivity heterogeneous intrusion into a high-conductivity heterogeneous medium. Our algorithm accurately reconstructs the location, orientation and extent of the intrusion from the steady-state data only. Addition of transient measurements of hydraulic head improves the parameter estimation, accurately reconstructing the conductivity field in the vicinity of observation locations. This article is protected by copyright. All rights reserved.
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  • 24
    Publication Date: 2015-06-04
    Description: Human societies are increasingly altering the water and biogeochemical cycles to both improve ecosystem productivity and reduce risks associated with the unpredictable variability of climatic drivers. These alterations, however, often cause large negative environmental consequences, raising the question as to how societies can ensure a sustainable use of natural resources for the future. Here we discuss how ecohydrological modeling may address these broad questions with special attention to agroecosystems. The challenges related to modeling the two-way interaction between society and environment are illustrated by means of a dynamical model in which soil and water quality supports the growth of human society but is also degraded by excessive pressure, leading to critical transitions and sustained societal growth-collapse cycles. We then focus on the coupled dynamics of soil water and solutes (nutrients or contaminants), emphasizing the modeling challenges, presented by the strong nonlinearities in the soil and plant system and the unpredictable hydro-climatic forcing, that need to be overcome to quantitatively analyze problems of soil water sustainability in both natural and agricultural ecosystems. We discuss applications of this framework to problems of irrigation, soil salinization, and fertilization and emphasize how optimal solutions for large-scale, long-term planning of soil and water resources in agroecosystems under uncertainty could be provided by methods from stochastic control, informed by physically and mathematically sound descriptions of ecohydrological and biogeochemical interactions. This article is protected by copyright. All rights reserved.
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  • 25
    Publication Date: 2015-06-04
    Description: Water resource management (WRM) through dams or reservoirs is worldwide necessary to support key human-related activities, ranging from hydropower production to water allocation and flood risk mitigation. Designing of reservoir operations aims primarily to fulfil the main purpose (or purposes) for which the structure has been built. However, it is well known that reservoirs strongly influence river geomorphic processes, causing sediment deficits downstream, altering water and sediment fluxes, leading to river bed incision and causing infrastructure instability and ecological degradation. We propose a framework that, by combining physically based modelling, surrogate modelling techniques and Multi-Objective (MO) optimization, allows to include fluvial geomorphology into MO optimization whose main objectives is the maximization of hydropower revenue and the minimization of river bed degradation. The case study is a run-of-the-river power plant on the River Po (Italy). A 1D mobile-bed hydro-morphological model simulated the river bed evolution over a ten year horizon for alternatives operation rules of the power plant. The knowledge provided by such a physically based model is integrated into a MO optimization routine via surrogate modelling using the response surface methodology. Hence, this framework overcomes the high computational costs that so far hindered the integration of river geomorphology into WRM. We provided numerical proof that river morphologic processes and hydropower production are indeed in conflict, but that the conflict may be mitigated with appropriate control strategies. This article is protected by copyright. All rights reserved.
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  • 26
    Publication Date: 2015-06-04
    Description: This paper addresses how much flood water can be conserved for use after the flood season through the operation of reservoir by taking into account the residual flood control capacity (the difference between flood conveyance capacity and the expected inflow in a lead time). A two-stage model for dynamic control of the flood limited water level (the maximum allowed water level during the flood season, DC-FLWL) is established considering forecast uncertainty and acceptable flood risk. It is found that DC-FLWL is applicable when the reservoir inflow ranges from small to medium levels of the historical records, while both forecast uncertainty and acceptable risk in the downstream affect the feasible space of DC-FLWL. As forecast uncertainty increases (under a given risk level) or as acceptable risk level decreases (under a given forecast uncertainty level), the minimum required safety margin for flood control increases, and the chance for DC-FLWL decreases. The derived hedging rules from the modeling framework illustrate either the dominant role of water conservation or flood control or the tradeoff between the two objectives under different levels of forecast uncertainty and acceptable risk. These rules may provide useful guidelines for conserving water from flood, especially in the area with heavy water stress. The analysis is illustrated via a case study with a real-world reservoir in northeastern China. This article is protected by copyright. All rights reserved.
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  • 27
    Publication Date: 2015-08-04
    Description: Inhibitory effects of high glucose and ethanol concentrations on ethanol production from wheat enzymatic hydrolysate by zygomycetes fungus Mucor hiemalis were investigated and modeled. Ethanol yield was decreased by increasing glucose concentration from 70 to 120 g.l -1 . Among different kinetic models, i.e., linear, Emerson, and modified Williams, modified Williams model was successfully described the fungal growth kinetics. Considering the inhibitory effect of glucose, a new model was developed for describing the rate of ethanol production. Moreover, the inhibitory effect of ethanol on ethanol yield, Y p/x , was modeled. The model prediction was successfully covered the experimental data.
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  • 28
    Publication Date: 2015-08-05
    Description: We present a co-evolutionary view of hydrologic systems, revolving around feedbacks between environmental and social processes operating across different time scales. This brings to the fore an emphasis on emergent phenomena in changing water systems, such as the levee effect, adaptation to change, system lock-in, and system collapse due to resource depletion. Changing human values play a key role in the emergence of these phenomena and should therefore be considered as internal to the system. Guidance is provided for the framing and modeling of these phenomena to test alternative hypotheses about how they arose. A plurality of co-evolutionary models, from stylized to comprehensive system-of-system models, may assist strategic water management for long time scales through facilitating stakeholder participation, exploring the possibility space of alternative futures, and helping to synthesize the observed dynamics in a wide range of case studies. Future research opportunities lie in exploring emergent phenomena arising from time scale interactions through historical, comparative and process studies of human-water feedbacks. This article is protected by copyright. All rights reserved.
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  • 29
    Publication Date: 2015-08-05
    Description: ABSTRACT Multiphase-fluid distribution and flow is inherent in numerous areas of hydrology. Yet, pore-scale characterization of transitions between two and three immiscible-fluids is limited. The objective of this study was to examine the impact of such transitions on the pore-scale configuration of organic liquid in a multi-fluid system comprising natural porous media. Three-dimensional images of an organic liquid (trichloroethene) in two-phase (organic-liquid/water) and three-phase (air/organic-liquid/water) systems were obtained using X-ray microtomography before and after drainage and imbibition. Upon transition from a two-phase to a three-phase system, a significant portion of the organic liquid (intermediate wetting fluid) was observed to exist as lenses and films in contact with air (nonwetting fluid). In these cases, the air was either encased by or contiguous to the organic liquid. The presence of air resulted in an increase in the surface-area-to-volume ratios for the organic-liquid blobs. Upon imbibition, the air was displaced downgradient, and concomitantly, the morphology of the organic-liquid blobs no longer in contact with air reverted to that characteristic of a two-phase distribution (i.e., more spherical blobs and ganglia). This change in morphology resulted in a reduction in the surface-area-to-volume ratio. These results illustrate the impact of transitions between two-phase and three-phase conditions on fluid configuration, and they demonstrate the malleable nature of fluid configuration under dynamic, multiphase-flow conditions. The results have implications for characterizing and modeling pore-scale flow and mass-transfer processes. This article is protected by copyright. All rights reserved.
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  • 30
    Publication Date: 2015-08-05
    Description: We performed power-spectral analyses on 133 globally distributed lake-level time series after removing annual variability. Lake-level power spectra are found to be power-law functions of frequency over the range of 20 days -1 to 27 years -1 , suggesting that lake levels are globally a f -β -type noise. The spectral exponent (β), i.e. the best-fit slope of the logarithm of the power spectrum to the logarithm of frequency, is a nonlinear function of lake surface area, indicating that lake size is an important control on the magnitude of water-level variability over the range of time scales we considered. A simple cellular model for lake-level fluctuations that reproduces the observed spectral-scaling properties is presented. The model (an adaptation of a surface-growth model with random deposition and relaxation) is based on the equations governing flow in an unconfined aquifer with stochastic inputs and outputs of water (e.g. random storms). The agreement between observation and simulation suggests that lake surface area, spatio-temporal stochastic forcing, and diffusion of the groundwater table are the primary factors controlling lake water-level variability in natural (unmanaged) lakes. Water-level variability is generally considered to be a manifestation of climate trends or climate change, yet our work shows that an input with short or no memory (i.e. weather) gives rise to a long-memory non-stationary output (lake water-level). This work forms the basis for a null hypothesis of lake water-level variability that should be disproven before water-level trends are to be attributed to climate. This article is protected by copyright. All rights reserved.
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  • 31
    Publication Date: 2015-07-29
    Description: Describing convective nonwetting phase flow in unsaturated porous media requires knowledge of the nonwetting phase relative permeability. This study was conducted to formulate and derive a generalized expression for the nonwetting phase relative permeability via combining with the Kosugi water retention function. This generalized formulation is then used to flexibly investigate the Burdine, Mualem and Alexander and Skaggs models' prediction accuracy for relative nonwetting phase permeability. The model and data comparison results show that these three permeability models, if used in their original form, but applied to the nonwetting phase, could not predict the experimental data well. The optimum pore tortuosity and connectivity value is thus obtained for the improved prediction of relative nonwetting phase permeability. As a result, the effective parametrization of (α,β,η) parameters in the modified Burdine, modified Mualem and modified Alexander and Skaggs permeability models were found to be (2.5, 2, 1), (2, 1, 2) and (2.5, 1, 1), respectively. These three suggested models display the highest accuracy among the nine relative permeability models investigated in this study. However, the corresponding discontinuous nonwetting phase and the liquid film flow should be accounted for in future for the improved prediction of nonwetting phase relative permeability at very high and very low water saturation range, respectively. This article is protected by copyright. All rights reserved.
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  • 32
    Publication Date: 2015-07-29
    Description: A new optical remote sensing technique for estimating water depth from an oblique camera view is described. The water surface and the bed were imaged simultaneously to create time-dependent maps of the water surface velocities and the bed elevations that can be used to validate numerical models at high spatial and temporal resolution. The technique was applied in a sandy meander bend at the University of Minnesota Saint Anthony Falls Laboratory Outdoor StreamLab. The root mean square differences between optical estimates of the bed and in situ observations ranged between 0.01 and 0.03 m. Mean bedform wavelength was 0.73 m and mean crest height was 0.07 m, but both varied with distance around the meander bend. Bedform classification varied with distance downstream, and sinuosity of bedforms varied with local radius of curvature. Bedform roughness scaled similarly to other natural riverine environments although wavelength and height magnitude and variability were larger than predicted by empirical formulations for straight reaches. Bedform translation rate varied between 1 and 5 mm s −1 . Estimates of velocity from particle image velocimetry (PIV) on the water surface were ∼10% higher than in situ observations collected ∼0.05 m below the water surface. Using the PIV observations to drive simple equations for bedload sediment flux, we explained up to 72% of the observed variance in downstream sediment flux. The new methodology described here provides non-intrusive, high spatial and temporal resolution measurements of both the bed and the flow. This article is protected by copyright. All rights reserved.
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  • 33
    Publication Date: 2015-07-29
    Description: We study the influence of topography on groundwater fluxes and water table depths across the Contiguous United States (CONUS). Groundwater tables are often conceptualized as subdued replicas of topography. While it is well known that groundwater configuration is also controlled by geology and climate, nonlinear interactions between these drivers within large real world systems are not well understood and are difficult to characterize given sparse groundwater observations. We address this limitation using the fully integrated physical hydrology model ParFlow to directly simulate groundwater fluxes and water table depths within a complex heterogeneous domain that incorporates all three primary groundwater drivers. Analysis is based on a first of its kind, continental scale, high-resolution (1km), groundwater-surface water simulation spanning more than 6.3 million km 2 . Results show that groundwater fluxes are most strongly driven by topographic gradients (as opposed to gradients in pressure head) in humid regions with small topographic gradients or low conductivity. These regions are generally consistent with the topographically controlled groundwater regions identified in previous studies. However, we also show that areas where topographic slopes drive groundwater flux do not generally have strong correlations between water table depth and elevation. Nonlinear relationships between topography and water table depth are consistent with groundwater flow systems that are dominated by local convergence and could also be influenced by local variability in geology and climate. One of the strengths of the numerical modeling approach is its ability to evaluate continental scale groundwater behavior at a high resolution not possible with other techniques. This article is protected by copyright. All rights reserved.
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  • 34
    Publication Date: 2015-08-08
    Description: In this study experimental mass transfer data and literature data of airlift loop reactors are analyzed concerning an effect of gas-phase residence time on the volumetric mass transfer coefficient k L a. It becomes evident that a neglect of the oxygen depletion can be regarded as a diminishment of the mass transfer driving force. The latter is found to be an important cause of the mass transfer dependency on the actual apparatus height of airlift loop reactors. Therefore a new correlation is presented which describes the volumetric mass transfer coefficients of airlift loop reactors by including the effect of gas-phase transient component concentration depletion. In this work two geometrically similar experimental apparatuses of different absolute size are utilized. Both of them are driven as airlift loop reactors with aerated concentric draft tube. The operating method is schematically illustrated in Fig. 3. The essential geometric data of the reactors is listed in Tab. 1.
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  • 35
    Publication Date: 2015-08-08
    Description: Monolithic honeycomb reactors are characterized by small parallel channels, which make them an interesting approach to be applied as microstructured reactors. Besides the established manufacturing of ceramic honeycombs, these structures exhibit excellent mass transfer characteristics for multiphase reactions combined with degrees of freedom in the structural design. In this contribution the potential of monolithic honeycomb reactors operated in the beneficial slug flow regime is evaluated for heterogeneously catalyzed gas-liquid reactions. Therefore, results of the Fischer-Tropsch synthesis and hydrogenation of glucose to sorbitol were analyzed in order to obtain a more generalized picture of the interaction between mass transfer and reaction in small channels operated in multiphase flow.
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  • 36
    Publication Date: 2015-08-08
    Description: The concept of a multi-stage microstructured (MM) reactor has been tested in the bench-scale rig for combined steam and CO 2 reforming of methane (RM). In this reactor type the RM reaction is carried out in a series of adiabatic catalytic reaction steps with heat supply through fin-plate heat exchangers placed between the stages. RM reaction has been performed over a rhodium based catalyst in form of pellets. The experimental results have been described with a reaction engineering model that can be used as basis for model-supported scale-up. This paper describes an intermediate step in the development of the integrated reactor for thermal integration of oxidative coupling and reforming of methane. Conversion and yield near thermodynamical equilibrium have been achieved. Experiments confirmed advantages of the MM reactor against wall-coated micro reactors.
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  • 37
    Publication Date: 2015-08-08
    Description: Hydrology is an integrative discipline linking the broad array of water-related research with physical, ecological, and social sciences. The increasing breadth of hydrological research, often where subdisciplines of hydrology partner with related sciences, reflects the central importance of water to environmental science, while highlighting the fractured nature of the discipline itself. This lack of coordination among hydrologic subdisciplines has hindered the development of hydrologic theory and integrated models capable of predicting hydrologic partitioning across time and space. The recent development of the concept of the critical zone (CZ), an open system extending from the top of the canopy to the base of groundwater, brings together multiple hydrological subdisciplines with related physical and ecological sciences. Observations obtained by CZ researchers provide a diverse range of complementary process and structural data to evaluate both conceptual and numerical models. Consequently, a cross-site focus on “critical zone hydrology” has potential to advance the discipline of hydrology and to facilitate the transition of CZ observatories into a research network with immediate societal relevance. Here we review recent work in catchment hydrology and hydrochemistry, hydrogeology, and ecohydrology that highlights a common knowledge gap in how precipitation is partitioned in the critical zone: “ how is the amount, routing, and residence time of water in the subsurface related to the biogeophysical structure of the CZ? ” Addressing this question will require coordination among hydrologic subdisciplines and interfacing sciences, and catalyze rapid progress in understanding current CZ structure and predicting how climate and land cover changes will affect hydrologic partitioning. This article is protected by copyright. All rights reserved.
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  • 38
    Publication Date: 2015-08-12
    Description: In the last decades significant technological advances together with improved modeling capabilities fostered a rapid development of geophysical monitoring techniques in support of hydrological modeling. Geophysical monitoring offers the attractive possibility to acquire spatially distributed information on state variables. These provide complementary information about the functioning of the hydrological system to that provided by standard hydrological measurements, which are either intrinsically local or the result of a complex spatial averaging process. Soil water content is an example of state variable, which is relatively simple to measure pointwise (locally) but with a vanishing constraining effect on catchment-scale modeling, while streamflow data, the typical hydrological measurement, offer limited possibility to disentangle the controlling processes. The objective of this work is to analyze the advantages offered by coupling traditional hydrological data with unconventional geophysical information in inverse modeling of hydrological systems. In particular, we explored how the use of time-lapse, spatially distributed microgravity measurements may improve the conceptual model identification of a topographically complex Alpine catchment (the Vermigliana catchment, South-Eastern Alps, Italy). The inclusion of microgravity data resulted in a better constraint of the inversion procedure and an improved capability to identify limitations of concurring conceptual models to a level that would be impossible relying only on streamflow data. This allowed for a better identification of model parameters and a more reliable description of the controlling hydrological processes, with a significant reduction of uncertainty in water storage dynamics with respect to the case when only streamflow data are used. This article is protected by copyright. All rights reserved.
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  • 39
    Publication Date: 2015-08-15
    Description: We present new measurements of bedload tracer transport in a mountain stream over several snowmelt seasons. Cumulative displacements were measured using passive tracers, which consisted of gravel and cobbles embedded with radio frequency identification tags. The timing of bedload motion during eleven transporting events was quantified with active tracers, i.e., accelerometer-embedded cobbles. Probabilities of cobble transport increased with discharge above a threshold, and exhibited slight to moderate hysteresis during snowmelt hydrographs. Dividing cumulative displacements by the number of movements recorded by each active tracer constrained average step lengths. Average step lengths increased with discharge, and distributions of average step lengths and cumulative displacements were thin-tailed. Distributions of rest times followed heavy-tailed power law scaling. Rest time scaling varied somewhat with discharge and with the degree to which tracers were incorporated into the stream bed. The combination of thin-tailed displacement distributions and heavy-tailed rest time distributions predict superdiffusive dispersion. This article is protected by copyright. All rights reserved.
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  • 40
    Publication Date: 2015-08-15
    Description: Gas transfer processes are fundamental to the biogeochemical and water quality functions of wetlands, yet there is limited knowledge of the rates and pathways of soil - atmosphere exchange for gases other than oxygen and methane (CH 4 ). In this study we use a novel push-pull technique with sulfur hexafluoride (SF 6 ) and helium (He) as dissolved gas tracers to quantify the kinetics of root-mediated gas transfer, which is a critical efflux pathway for gases from wetland soils. This tracer approach disentangles the effects of physical transport from simultaneous reaction in saturated, vegetated wetland soils. We measured significant seasonal variation in first-order gas exchange rate constants, with smaller spatial variations between different soil depths and vegetation zones in a New Jersey tidal marsh. Gas transfer rates for most biogeochemical trace gases are expected to be bracketed by the rate constants for SF 6 and He, which ranged from ∼10 −2 to 2x10 −1 h −1 at our site. A modified Damköhler number analysis is used to evaluate the balance between biochemical reaction and root-driven gas exchange in governing the fate of environmental trace gases in rooted, anaerobic soils. This approach confirmed the importance of plant gas transport for CH 4 , and showed that root-driven transport may affect nitrous oxide (N 2 O) balances in settings where N 2 O reduction rates are slow This article is protected by copyright. All rights reserved.
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  • 41
    Publication Date: 2015-08-15
    Description: Measuring vertically nested temperatures at the streambed interface poses practical challenges that are addressed here with a new discrete subsurface temperature profiling probe. We describe a new temperature probe and its application for heat as a tracer investigations to demonstrate the probe's utility. Accuracy and response time of temperature measurements made at 6 discrete depths in the probe were analyzed in the laboratory using temperature bath experiments. We find the temperature probe to be an accurate and robust instrument that allows for easily installation and long-term monitoring in highly variable environments. Because the probe is inexpensive and versatile, it is useful for many environmental applications that require temperature data collection for periods of several months in environments that are difficult to access or require minimal disturbance. This article is protected by copyright. All rights reserved.
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  • 42
    Publication Date: 2015-09-11
    Description: This short review describes photocatalytic vs photosensitizing materials to be used respectively for gas-phase photooxidation and photo-oxygenation. The reactive oxygen species specific to photocatalysis and to photosensitization are summarized. Various kinds of gas-phase reactors and of photocatalytic materials are described in order to illustrate the great number of possible configurations and conditions of use. Some efforts towards standardization of gas-phase photocatalytic reactors devoted to indoor- or outdoor-air treatment are mentioned. Some examples of use of singlet oxygen in solvent-free photooxygenation reaction of volatile sulfides are given together with the properties of silica-based photosensitizing materials.
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  • 43
    Publication Date: 2015-09-11
    Description: Fluorine and fluorine-containing groups are omnipresent in pharmaceuticals, agrochemicals and many other high-value chemical products like liquid crystals and organic electronics. The unique properties of fluorine resulting from its tremendously high electronegativity make this element a key player in the quest of enabling new and advanced qualities for chemical compounds and materials. With the advent of fluorinating reagents a great diversity of synthetic methodologies has been developed to incorporate fluorine or fluorine-containing groups into small molecules with high conversion and selectivity. Especially photochemically catalyzed fluorination reactions proved their potential for the synthesis of fluorine-containing fine chemicals due to their mild reaction conditions. This tutorial review gives an overview of recently published synthesis strategies that use (visible-) light-absorbing catalysts for the activation of fluorinating reagents. A special focus is made on the use of continuous-flow microreactors for photochemically catalyzed fluorination reactions due to the excellent utilization of this reactor equipment for photochemistry.
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  • 44
    Publication Date: 2015-09-11
    Description: This manuscript addresses the evaluation of photocatalytic efficiency using Quantum Yields (QY) and the “Photochemical Thermodynamic Efficiency Factor” (PTEF). While the QY can be considered as an early photocatalytic reactor efficiency factor, developed in the 80’s, the PTEF was first introduced by Serrano and de Lasa in 1997 [29]. The PTEF allows establishing reactor efficiency as the ratio of utilized enthalpy for the formation of consumed OH • free radicals over the absorbed photon energy. In all cases, a key consideration for the evaluation of efficiency factors is the establishment of macroscopic energy balances together with an accurate assessment of evolved and absorbed photons. Of considerable help, as well, are the experimental devices developed at the Chemical Reactor Engineering Centre (CREC)-University of Western Ontario laboratories. Furthermore, photoconversion kinetics is a required information for the calculation of the OH • consumption rates and the establishment of the related kinetic parameters. In this respect, de Lasa et al (2005) [6] postulated a unified “in series-parallel” model for the kinetics in photocatalytic conversion. Until today, both PTEFs and QYs have been used by CREC-UWO researchers for efficiency calculations in photocatalytic reactors for the decontamination of air, water and hydrogen production. This methodology is very relevant, in particular, for the assessment of the effects of reactor scale, reactor configuration, irradiation source, type of photocatalyst and model pollutant compounds.
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  • 45
    Publication Date: 2015-09-12
    Description: Nanoparticle deposition behavior observed at the Darcy scale represents an average of the processes occurring at the pore scale. Hence, the effect of various pore-scale parameters on nanoparticle deposition can be understood by studying nanoparticle transport at pore scale and upscaling the results to the Darcy scale. In this work, correlation equations for the deposition rate coefficients of nanoparticles in a cylindrical pore are developed as a function of nine pore-scale parameters: the pore radius, nanoparticle radius, mean flow velocity, solution ionic strength, viscosity, temperature, solution dielectric constant, and nanoparticle and collector surface potentials. Based on dominant processes, the pore space is divided into three different regions, namely, bulk, diffusion, and potential regions. Advection-diffusion equations for nanoparticle transport are prescribed for the bulk and diffusion regions, while the interaction between the diffusion and potential regions is included as a boundary condition. This interaction is modeled as a first-order reversible kinetic adsorption. The expressions for the mass transfer rate coefficients between the diffusion and the potential regions are derived in terms of the interaction energy profile. Among other effects, we account for nanoparticle-collector interaction forces on nanoparticle deposition. The resulting equations are solved numerically for a range of values of pore-scale parameters. The nanoparticle concentration profile obtained for the cylindrical pore is averaged over a moving averaging volume within the pore in order to get the 1D concentration field. The latter is fitted to the 1D advection-dispersion equation with an equilibrium or kinetic adsorption model to determine the values of the average deposition rate coefficients. In this study, pore-scale simulations are performed for three values of Péclet number, Pe = 0.05, 5 and 50. We find that under unfavorable conditions, the nanoparticle deposition at pore scale is best described by an equilibrium model at low Péclet numbers ( Pe = 0.05), and by a kinetic model at high Péclet numbers ( Pe = 50). But, at an intermediate Pe (e.g., near Pe = 5), both equilibrium and kinetic models fit the 1D concentration field. Correlation equations for the pore-averaged nanoparticle deposition rate coefficients under unfavorable conditions are derived by performing a multiple-linear regression analysis between the estimated deposition rate coefficients for a single pore and various pore-scale parameters. The correlation equations, which follow a power law relation with nine pore-scale parameters, are found to be consistent with the column-scale and pore-scale experimental results, and qualitatively agree with the colloid filtration theory. These equations can be incorporated into pore network models to study the effect of pore-scale parameters on nanoparticle deposition at larger length scales such as Darcy scale. This article is protected by copyright. All rights reserved.
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  • 46
    Publication Date: 2015-09-12
    Description: Safe drinking water is critical to human health and development. In rural sub-Saharan Africa, most improved water sources are boreholes with handpumps; studies suggest that up to one third of these handpumps are non-functional at any given time. This work presents findings from a secondary analysis of cross-sectional data from 1509 water sources in 570 communities in the rural Greater Afram Plains (GAP) region of Ghana; one of the largest studies of its kind. 79.4% of enumerated water sources were functional when visited; in multivariable regressions, functionality depended on source age, management, the number of other sources in the community, and the district. A Bayesian network (BN) model developed using the same dataset found strong dependencies of functionality on implementer, pump type, management, and the availability of tools, with synergistic effects from management determinants on functionality, increasing the likelihood of a source being functional from a baseline of 72% to more than 97% with optimal management and available tools. We suggest that functionality may be a dynamic equilibrium between regular breakdowns and repairs, with management a key determinant of repair rate. Management variables may interact synergistically in ways better captured by BN analysis than by logistic regressions. These qualitative findings may prove generalizable beyond the study area, and may offer new approaches to understanding and increasing handpump functionality and safe water access. This article is protected by copyright. All rights reserved.
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  • 47
    Publication Date: 2015-09-12
    Description: Process controls on water, sediment, nutrient and organic carbon exports from the landscape through runoff are not fully understood. This paper provides analyses from 446 sites worldwide to evaluate the impact of environmental factors (MAP and MAT: mean annual precipitation and temperature; CLAY and BD: soil clay content and bulk density; S: slope gradient and LU: land use) on annual exports (R C : runoff coefficients; SL: sediment loads; TOC L : organic carbon losses; TN L : nitrogen losses and TP L : phosphorus losses) from different spatial scales. R C was found to increase, on average, from 18% at local scale (in headwaters), 25% at micro and subcatchment scale (mid-reaches) to 41% at catchment scale (lower reaches of river basins) in response to multiple factors. SL increased from microplots (468 g m −2 yr −1 ) to plots (901 g m −2 yr −1 ), accompanied by decreasing TOC L and TN L . Climate was a major control masking the effects of other factors. For example, R C , SL, TOC L , TN L and TP L tended to increase with MAP at all spatial scales. These variables, however, decreased with MAT. The impact of CLAY, BD, LU and S on erosion variables was largely confined to the hillslope scale, where R C, SL and TOC L decreased with CLAY, while TNL and TP L increased. The results contribute to better understanding of water, nutrient and carbon cycles in terrestrial ecosystems, and should inform river basin modelling and ecosystem management. The important role of spatial climate variability points to a need for comparative research in specific environments at nested spatio-temporal scales. This article is protected by copyright. All rights reserved.
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  • 48
    Publication Date: 2015-09-17
    Description: The wettability of CO 2 -brine-rock systems will have a major impact on the management of carbon sequestration in subsurface geological formations. Recent contact angle measurement studies have reported sensitivity in wetting behaviour of this system to pressure, temperature and brine salinity. We report observations of the impact of reservoir conditions on the capillary pressure characteristic curve and and relative permeability of a single Berea sandstone during drainage - CO 2 displacing brine - through effects on the wetting state. Eight reservoir condition drainage capillary pressure characteristic curves were measured using CO 2 and brine in a single fired Berea sandstone at pressures (5 to 20 MPa), temperatures (25 to 50°C) and ionic strengths (0 to 5 mol kg −1 NaCl). A ninth measurement using a N 2 -water system provided a benchmark for capillarity with a strongly water wet system. The capillary pressure curves from each of the tests were found to be similar to the N 2 -water curve when scaled by the interfacial tension. Reservoir conditions were not found to have a significant impact on the capillary strength of the CO 2 -brine system during drainage through a variation in the wetting state. Two steady-state relative permeability measurements with CO 2 and brine and one with N 2 and brine similarly show little variation between conditions, consistent with the observation that the CO 2 -brine-sandstone system is water wetting and multiphase flow properties invariant across a wide range of reservoir conditions. This article is protected by copyright. All rights reserved.
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  • 49
    Publication Date: 2015-09-17
    Description: Hillslope-scale rainfall-runoff processes leading to a fast catchment response are not explicitly included in land surface models (LSMs) for use in earth system models (ESMs) due to computational constraints. This study presents a hybrid-3D hillslope hydrological model (h3D) that couples a 1D vertical soil column model with a lateral pseudo-2D saturated zone and overland flow model for use in ESMs. By representing vertical and lateral responses separately at different spatial resolutions, h3D is computationally efficient. The h3D model was first tested for three different hillslope planforms (uniform, convergent and divergent). We then compared h3D (with single and multiple soil columns) with a complex physically-based 3D model and a simple 1D soil moisture model coupled with an unconfined aquifer (as typically used in LSMs). It is found that simulations obtained by the simple 1D model vary considerably from the complex 3D model and are not able to represent hillslope-scale variations in the lateral flow response. In contrast, the single soil column h3D model shows a much better performance and saves computational time by 2-3 orders of magnitude compared with the complex 3D model. When multiple vertical soil columns are implemented, the resulting hydrological responses (soil moisture, water table depth, and baseflow along the hillslope) from h3D are nearly identical to those predicted by the complex 3D model, but still saves computational time. As such, the computational efficiency of the h3D model provides a valuable and promising approach to incorporating hillslope-scale hydrological processes into continental and global-scale ESMs. This article is protected by copyright. All rights reserved.
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  • 50
    Publication Date: 2015-09-17
    Description: We investigated potential source areas of dissolved organic carbon (DOC) in headwater streams by examining DOC concentrations in lysimeter, shallow well, and streamwater samples from a reference catchment at the Hubbard Brook Experimental Forest. These observations were then compared to high frequency temporal variations in fluorescent dissolved organic matter (FDOM) at the catchment outlet and the predicted spatial extent of shallow groundwater in soils throughout the catchment. While near-stream soils are generally considered a DOC source in forested catchments, DOC concentrations in near-stream groundwater were low (mean = 2.4 mg/L, standard error = 0.6 mg/L), less than hillslope groundwater farther from the channel (mean = 5.7 mg/L, standard error = 0.4 mg/L). Furthermore, water tables in near-stream soils did not rise into the carbon rich upper B or O horizons even during events. In contrast, soils below bedrock outcrops near channel heads where lateral soil formation processes dominate had much higher DOC concentrations. Soils immediately downslope of bedrock areas had thick eluvial horizons indicative of leaching of organic materials, Fe, and Al and had similarly high DOC concentrations in groundwater (mean = 14.5 mg/L, standard error = 0.8 mg/L). Flow from bedrock outcrops partially covered by organic soil horizons produced the highest groundwater DOC concentrations (mean = 20.0 mg/L, standard error = 4.6 mg/L) measured in the catchment. Correspondingly, streamwater in channel heads sourced in part by shallow soils and bedrock outcrops had the highest stream DOC concentrations measured in the catchment. Variation in FDOM concentrations at the catchment outlet followed water table fluctuations in shallow to bedrock soils near channel heads. We show that shallow hillslope soils receiving runoff from organic matter-covered bedrock outcrops may be a major source of DOC in headwater catchments in forested mountainous regions where catchments have exposed or shallow bedrock near channel heads. This article is protected by copyright. All rights reserved.
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  • 51
    Publication Date: 2015-09-17
    Description: ABSTRACT Multiple scenarios of upward CO 2 migration driven by both injection-induced pressure and buoyancy force were investigated in a horizontally and vertically stratified core utilizing a core-flooding system with a 2D X-ray scanner. Two reservoir type scenarios were considered: (1) the terrestrial reservoir scenario (10 MPa and 50°C), where CO 2 exists in a supercritical state and (2) the deep-sea sediment reservoir scenario (28 MPa and 25°C), where CO 2 is stored in the liquid phase. The core-flooding experiments showed a 36% increase in migration rate in the vertical core setting compared with the horizontal setting, indicating the significance of the buoyancy force under the terrestrial reservoir scenario. Under both reservoir conditions, the injected CO 2 tended to find a preferential flow path (low capillary entry pressure and high-permeability (high- k ) path) and bypass the unfavorable pathways, leaving low CO 2 saturation in the low-permeability (low- k ) layers. No distinctive fingering was observed as the CO 2 moved upward, and the CO 2 movement was primarily controlled by media heterogeneity. The CO 2 saturation in the low- k layers exhibited a more sensitive response to injection rates, implying that the increase in CO 2 injection rates could be more effective in terms of storage capacity in the low- k layers in a stratified reservoir. Under the deep-sea sediment condition, the storage potential of liquid CO 2 was more than twice as high as that of supercritical CO 2 under the terrestrial reservoir scenario. In the end, multiphase transport simulations were conducted to assess the effects of heterogeneity on the spatial variation of pressure build-up, CO 2 saturation and CO 2 flux. Finally, we showed that a high gravity number () tended to be more influenced by the heterogeneity of the porous media. This article is protected by copyright. All rights reserved.
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  • 52
    Publication Date: 2015-09-17
    Description: Lake water storage change (Δ S w ) is an important indicator of the hydrologic cycle and greatly influences lake expansion/shrinkage over the Tibetan Plateau (TP). Accurate estimation of Δ S w will contribute to improved understanding of lake variations in the TP. Based on a water balance, this study explored the variations of Δ S w for the Lake Selin Co (the largest closed lake on the TP) during 2003-2012 using the Water and Energy Budget-based Distributed Hydrological Model (WEB-DHM) together with two different evapotranspiration (ET) algorithms (the Penman-Monteith method and a simple sublimation estimation approach for water area in unfrozen and frozen period). The contributions of basin discharge and climate causes to the Δ S w are also quantitatively analyzed. The results showed that WEB-DHM could well reproduce daily discharge, the spatial pattern and basin-averaged values of MODIS land surface temperature (LST) during nighttime and daytime. Compared with the ET reference values estimated from the basin-wide water balance, our ET estimates showed better performance than three global ET products in reproducing basin-averaged ET. The modeled ET at point scale matches well with short-term in situ daily measurements (RMSE = 0.82 mm/day). Lake inflows and precipitation over the water area had stronger relationships with Δ S w in the warm season and monthly scale, whereas evaporation from the water area had remarkable effects on Δ S w in the cold season. The total contribution of the three factors to Δ S w was about 90%, and accounting for 49.5%, 22.1% and 18.3%, respectively. This article is protected by copyright. All rights reserved.
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  • 53
    Publication Date: 2015-09-17
    Description: Predicting hydro(geo)logical or environmental systems is subject to high levels of uncertainties, especially if appropriate data for model calibration are lacking. For subsurface systems, where data acquisition is cost intensive and time demanding, it is especially important to collect only those data that provide the largest amount of relevant information. The high expenses call for optimal experimental design, which is widely recognized for maximizing the efficiency of experiments. In model-based design of experiments, the analysis of the design efficiency and the resulting optimal design are based on the initial state of knowledge about the modeled system. Joint optimization of multi-measurement designs is a well known challenge and the usefulness of global optimization approaches is widely recognized in this context. However, we will show that the benefit for such global optimization becomes questionable when measurement data become available sequentially. Instead, the optimization effort should be invested within an interactive design approach. Today's fast telecommunication, global connectivity and high-performance computing allow to consider such interactive coupling. This study will use a synthetic case study to compare the standard en-bloc global optimization approach to two interactive design approaches. The approaches are implemented in a Bayesian framework and are compared based on their complexity and overall performance. The key conclusion confirms a previously untested presumption: for models that trigger nonlinear parameter inference problems, interaction (which may come at a loss of global optimization) is more beneficial than global optimization based on the initial state of knowledge (which typically implies the impossibility of interactivity). This article is protected by copyright. All rights reserved.
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  • 54
    Publication Date: 2015-09-17
    Description: ABSTRACT Environmental tracers provide information on groundwater age, recharge conditions, and flow processes which can be helpful for evaluating groundwater sustainability and vulnerability. Dissolved noble gas data have proven particularly useful in mountainous terrain because they can be used to determine recharge elevation. However, tracer-derived recharge elevations have not been utilized as calibration targets for numerical groundwater flow models. Herein we constrain and calibrate a regional groundwater flow model with noble-gas-derived recharge elevations for the first time. Tritium and noble gas tracer results improved the site conceptual model by identifying a previously uncertain contribution of mountain-block recharge from the Coast Mountains to an alluvial coastal aquifer in humid southwestern British Columbia. The revised conceptual model was integrated into a three-dimensional numerical groundwater flow model and calibrated to hydraulic head data in addition to recharge elevations estimated from noble gas recharge temperatures. Recharge elevations proved to be imperative for constraining hydraulic conductivity, recharge location and bedrock geometry, and thus minimizing model non-uniqueness. Results indicate that 45% of recharge to the aquifer is mountain-block recharge. A similar match between measured and modeled heads was achieved in a second numerical model that excludes the mountain block (no mountain block recharge), demonstrating that hydraulic head data alone are incapable of quantifying mountain block recharge. This result has significant implications for understanding and managing source water protection in recharge areas, potential effects of climate change, the overall water budget, and ultimately ensuring groundwater sustainability. This article is protected by copyright. All rights reserved.
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  • 55
    Publication Date: 2015-09-19
    Description: The probability that new hydraulically fractured wells drilled within the area of New York underlain by the Marcellus Shale will intersect existing an wellbore is calculated using a statistical model, which incorporates: the depth of a new fracturing well, the vertical growth of induced fractures, and the depths and locations of existing nearby wells. The model first calculates the probability of encountering an existing well in plan view and combines this with the probability of an existing well being at sufficient depth to intersect the fractured region. Average probability estimates for the entire region of New York underlain by the Marcellus Shale range from 0.00% to 3.45% based upon the input parameters used. The largest contributing parameter on the probability value calculated is the nearby density of wells meaning that due diligence by oil and gas companies during construction in identifying all nearby wells will have the greatest effect in reducing the probability of interwellbore communication. This article is protected by copyright. All rights reserved.
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  • 56
    Publication Date: 2015-09-19
    Description: The idea of complementary evaporative fluxes, first advanced by Bouchet in 1963 is reformulated as a general polynomial, satisfying boundary conditions based on strictly physical considerations. Experimental evidence supports the validity of the imposed constraints. Earlier complementary relationships are shown to be special cases which satisfy only one of the necessary conditions. The new formulation provides a more rigorous base for the complementary principle. This article is protected by copyright. All rights reserved.
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  • 57
    Publication Date: 2015-09-19
    Description: A levee failure occurred along the Secchia River, Northern Italy, on January 19, 2014, resulting in flood damage in excess of $500 Million. In response to this failure, immediate surveillance of other levees in the region led to the identification of a second breach developing on the neighboring Panaro River, where rapid mitigation efforts were successful in averting a full levee failure. The paired breach events that occurred along the Secchia and Panaro Rivers provided an excellent window on an emerging levee failure mechanism. In the Secchia River, by combining the information content of photographs taken from helicopters in the early stage of breach development and 10-cm resolution aerial photographs taken in 2010 and 2012, animal burrows were found to exist in the precise levee location where the breach originated. In the Panaro River, internal erosion was observed to occur at a location where a crested porcupine den was known to exist and this erosion led to the collapse of the levee top. This paper uses detailed numerical modeling of rainfall, river flow, and variably saturated flow in the levee to explore the hydraulic and geotechnical mechanisms that were triggered along the Secchia and Panaro Rivers by activities of burrowing animals leading to levee failures. As habitats become more fragmented and constrained along river corridors it is possible that this failure mechanism could become more prevalent and, therefore, will demand greater attention in both the design and maintenance of earthen hydraulic structures as well as in wildlife management. This article is protected by copyright. All rights reserved.
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  • 58
    Publication Date: 2015-09-19
    Description: Future water demand is a main consideration in water system management. Consequently, water demand models (WDMs) have evolved in past decades, identifying principal demand-generating factors and modeling their influence on water demand. Regional water systems serve consumers of various types (e.g., municipalities, farmers, industrial regions) and consumption patterns. Thus, one of the challenges in regional water demand modeling is the heterogeneity of the consumers served by the water system. When a high-resolution, regional WDM is desired, accounting for this heterogeneity becomes all the more important. This paper presents a novel approach to regional water demand modeling. The two-step approach includes aggregating the dataset into groups of consumers having similar consumption characteristics, and developing a WDM for each homogeneous group. The development of WDMs is widely applied in the literature and thus, the focus of this paper is to discuss the first step of data aggregation. The research hypothesis is that water consumption records in their original or transformed form can provide a basis for aggregating the dataset into groups of consumers with similar consumption characteristics. This paper presents a methodology for water consumption data clustering by comparing several data representation methods (termed Feature Vectors): monthly normalized average, monthly consumption coefficient of variation, a combination of the monthly average and monthly variation, and the autocorrelation coefficients of the consumption time-series. Clustering using solely normalized monthly average provided homogeneous and distinct clusters with respect to monthly consumption, which succeed in capturing different consumer characteristics (water use, geographical location) that were not specified a-priori. Clustering using the monthly coefficient of variation provided different, yet homogeneous clusters, clustering consumers characterized by similar variation trends that were closely related to consumer water use type. The concatenation of these two Feature Vectors provided further insight into the relationship between consumption patterns and variability of consumers. An autocorrelation Feature Vector provided results that can form a basis for constructing a time-series model that is based on a group of resembling time-series. The approaches presented here are steps towards utilizing the increasing amount of available water consumption data and data analysis techniques to facilitate the modeling of water demands in larger and heterogeneous regions with sufficient resolution. This article is protected by copyright. All rights reserved.
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  • 59
    Publication Date: 2015-09-22
    Description: Most of the human appropriation of freshwater resources is for agriculture. Water availability is a major constraint to mankind's ability to produce food. The notion of virtual water content ( VWC ), also known as crop water footprint, provides an effective tool to investigate the linkage between food and water resources as a function of climate, soil and agricultural practices. The spatial variability in the virtual water content of crops is here explored, disentagling its dependency on climate and crop yields, and assessing the sensitivity of VWC estimates to parameter variability and uncertainty. Here we calculate the virtual water content of four staple crops (i.e., wheat, rice, maize, and soybean) for the entire world developing a high-resolution (5 by 5 arc minute) model, and we evaluate the VWC sensitivity to input-parameters. We find that food production almost entirely depends on green water (〉90%), but, when applied, irrigation makes crop production more water efficient, thus requiring less water. The spatial variability of the VWC is mostly controlled by the spatial patterns of crop yields with an average correlation coefficient of 0.83. The results of the sensitivity analysis show that wheat is most sensitive to the length of the growing period, rice to reference evapotranspiration, maize and soybean to the crop planting date. The VWC sensitivity varies not only among crops, but also across the harvested areas of the world, even at the sub-national scale. This article is protected by copyright. All rights reserved.
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  • 60
    Publication Date: 2015-09-22
    Description: The dissolution rate of non-aqueous phase liquid (NAPL) often governs the remediation time frame at subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the non-wetting fluid. However, field evidence suggests that some waste sites might be organic-wet. Thus, formulations that assume the NAPL is non-wetting may be inappropriate for estimating the rates of NAPL dissolution. An exact solution to the Young-Laplace equation, assuming NAPL resides as pendular rings around the contact points of porous media idealized as spherical particles in a hexagonal close packing arrangement, is presented in this work to provide a theoretical prediction for NAPL-water interfacial area. This analytic expression for interfacial area is then coupled with an exact solution to the advection-diffusion equation in a capillary tube assuming Hagen-Poiseuille flow to provide a theoretical means of calculating the mass transfer rate coefficient for dissolution at the NAPL-water interface in an organic-wet system. A comparison of the predictions from this theoretical model with predictions from empirically-derived formulations from the literature for water-wet systems showed a consistent range of values for the mass transfer rate coefficient, despite the significant differences in model foundations (water-wetting vs NAPL-wetting, theoretical vs. empirical). This finding implies that, under these system conditions, the important parameter is interfacial area, with a lesser role played by NAPL configuration. This article is protected by copyright. All rights reserved.
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  • 61
    Publication Date: 2015-09-22
    Description: A number of important candidate CO 2 reservoirs exhibit sedimentary architecture reflecting fluvial deposition. Recent studies have led to new conceptual and quantitative models for sedimentary architecture in fluvial deposits over a range of scales that are relevant to CO 2 injection and storage. We used a geocellular modelling approach to represent this multi-scaled and hierarchical sedimentary architecture. With this model, we investigated the dynamics of CO 2 plumes, during and after injection, in such reservoirs. The physical mechanism of CO 2 trapping by capillary trapping incorporates a number of related processes, i.e. residual trapping, trapping due to hysteresis of the relative permeability, and trapping due to hysteresis of the capillary pressure. Additionally CO 2 may be trapped due to differences in capillary entry pressure for different textural sedimentary facies (e.g. coarser- vs. finer-grained cross-sets). The amount of CO 2 trapped by these processes depends upon a complex system of non-linear and hysteretic characteristic relationships including how relative permeability and capillary pressure vary with brine and CO 2 saturation. The results strongly suggest that representing small-scale features (decimeter to meter), including their organization within a hierarchy of larger-scale features, and representing their differences in characteristic relationships, can all be critical to understanding trapping processes in some important candidate CO 2 reservoirs. This article is protected by copyright. All rights reserved.
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  • 62
    Publication Date: 2015-09-22
    Description: Under changing environments, not only univariate but also multivariate hydrological series might become nonstationary. Nonstationarity, in forms of change-point or trend, has been widely studied for univariate hydrological series, while it attracts attention only recently for multivariate hydrological series. For multivariate series, two types of change-point need to be distinguished, i.e. change-point in marginal distributions and change-point in the dependence structure among individual variables. In this paper, a three-step framework is proposed to separately detect two types of change-point in multivariate hydrological series, i.e. change-point detection for individual univariate series, estimation of marginal distributions, and change-point detection for dependence structure. The last step is implemented using both the Cramér-von Mises statistic (CvM) method and the copula-based likelihood-ratio test (CLR) method. For CLR, three kinds of copula model (symmetric, asymmetric, and pair-copula) are employed to construct the dependence structure of multivariate series. Monte Carlo experiments indicate that CLR is far more powerful than CvM in detecting the change-point of dependence structure. This framework is applied to the trivariate flood series composed of annual maxima daily discharge (AMDD), annual maxima 3-day flood volume and annual maxima 15-day flood volume of the Upper Hanjiang River, China. It is found that each individual univariate flood series has a significant change-point; and the trivariate series presents a significant change-point in dependence structure due to the abrupt change in the dependence structure between AMDD and annual maxima 3-day flood volume. All these changes are caused by the construction of the Ankang Reservoir. This article is protected by copyright. All rights reserved.
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  • 63
    Publication Date: 2015-09-22
    Description: An output-feedback control strategy for pollution mitigation in combined sewer networks is presented. The proposed strategy provides means to apply model-based predictive control to large-scale sewer networks, in-spite of the lack of measurements at most of the network sewers. In previous works, the authors presented a hybrid linear control-oriented model for sewer networks together with the formulation of Optimal Control Problems (OCP) and State Estimation Problems (SEP). By iteratively solving these problems, preliminary Receding Horizon Control with Moving Horizon Estimation (RHC/MHE) results, based on flow measurements, were also obtained. In this work, the RHC/MHE algorithm has been extended to take into account both flow and water level measurements and the resulting control loop has been extensively simulated to assess the system performance according different measurement availability scenarios and rain events. All simulations have been carried out using a detailed physically-based model of a real case-study network as virtual reality. This article is protected by copyright. All rights reserved.
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  • 64
    Publication Date: 2015-09-22
    Description: This paper investigates nonpayment behavior in Guatemala. Determinants of nonpayment behavior are identified through zero-inflated negative binomial regression models in order to take into account particular distributional characteristics of the amount of outstanding payments. Findings indicate that nonpayment behavior is a demonstration of consumer dissatisfaction with current water services. The amount of outstanding bill payments also responds to system unreliability. Results also suggest that nonpayment behaviors are more prominent in community-managed systems than in municipal systems. No evidence was found on a potential relationship between nonpayment behavior and household income. Policy implications are discussed. This article is protected by copyright. All rights reserved.
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  • 65
    Publication Date: 2015-09-23
    Description: Photoinitiated crosslinking of multifunctional acrylic esters in polymeric binders was investigated based on digital imaging using the Computer to Plate (CtP) technology applying laser exposure at 830 nm in the near infrared (NIR). All coating components were applied as thin double layer film on Al-plates with an anodized surface. Materials exposed exhibit a sensitivity between 30-100 mJ/cm 2 . Processing of the exposed materials occurred in a weak aqueous alkaline bath. Generation of initiating radicals occurs by electron transfer from the excited state of the NIR-sensitizer to the radical generator – an onium salt. Several onium salts with distinct cation and anion pattern were synthesized. Iodonium salts derived from several borates and those with the bis(trifluoromethylsulfonyl)imide anion resulted in lithographic materials with high sensitivity. Photoinduced electron transfer plays a major function to generate initiating radicals by a sensitized mechanism but thermal events also influence sensitivity of the coating. Particular the radiationless deactivation of the NIR-sensitizer possesses a major function for selective release of heat. Internal conversion (〉85%) was the major deactivation pathway while a certain fraction of NIR-dye fluorescence (〈15%) was also available. Moreover, a line shape focused laser system with emission in the NIR (808 nm) was successfully used to bake the materials. This was initiated by the absorption of the NIR-dye embedded in the coating.
    Print ISSN: 0930-7516
    Electronic ISSN: 1521-4125
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 66
    Publication Date: 2015-09-25
    Description: Agricultural practices have altered watershed-scale dissolved organic matter (DOM) dynamics, including in-stream concentration, biodegradability, and total catchment export. However, mechanisms responsible for these changes are not clear, and field-scale processes are rarely directly linked to the magnitude and quality of DOM that is transported to surface water. In a small (12 ha) agricultural catchment in eastern Washington State, we tested the hypothesis that hydrologic connectivity in a catchment is the dominant control over the concentration and quality of DOM exported to surface water via artificial subsurface drainage. Concentrations of dissolved organic carbon (DOC) and humic-like components of DOM decreased while the Fluorescence Index and Freshness Index increased with depth through the soil profile. In drain discharge, these characteristics were significantly correlated with drain flow across seasons and years, with drain DOM resembling deep sources during low flow and shallow sources during high flow, suggesting that DOM from shallow sources bypasses removal processes when hydrologic connectivity in the catchment is greatest. Assuming changes in streamflow projected for the Palouse River (which contains the study catchment) under the A1B climate scenario (rapid growth, dependence on fossil fuel and renewable energy sources) apply to the study catchment, we project greater interannual variability in annual DOC export in the future, with significant increases in the driest years. This study highlights the variability in DOM inputs from agricultural soil to surface water on daily to interannual timescales, pointing to the need for a more nuanced understanding of agricultural impacts on DOM dynamics in surface water. This article is protected by copyright. All rights reserved.
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  • 67
    Publication Date: 2015-09-25
    Description: In basement catchments of sub-humid West Africa, baseflow is the main component of annual streamflow. However, the important heterogeneity of lithology hinders the understanding of baseflow generation processes. Since these processes are linked with water storage changes (WSCs) across the catchment, we propose the use of hybrid gravity data in addition to neutron probe-derived water content and water levels to monitor spatiotemporal WSC of a typical crystalline basement headwater catchment (16 ha) in Benin. These behaviors are shown to provide insights into hydrological processes in terms of water redistribution toward the catchment outlet. Hybrid gravimetry produces gravity change observations from time-lapse microgravity surveys coupled with gravity changes monitored at a base station using a superconducting gravimeter and/or an absolute gravimeter. A dense microgravity campaign (70 surveys of 14 stations) covering three contrasted years was set up with a rigorous protocol, leading to low uncertainties (〈 2.5 µGal) on station gravity determinations (with respect to the network reference station). Empirical orthogonal function analyses of both gravity changes and WSCs from neutron probe data show similar spatial patterns in the seasonal signal. Areas where storage and water table show a capping behavior (when data reach a plateau during the wet season), suggesting threshold-governed fast subsurface redistribution, are identified. This observed storage dynamics, together with geological structures investigated by electrical resistivity tomography and drill log analysis make it possible to derive a conceptual model for the catchment hydrology. This article is protected by copyright. All rights reserved.
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  • 68
    Publication Date: 2015-09-25
    Description: 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, and elements with low conductivity retards flow with discontinuous head. Baseflow interactions at the interface between groundwater and surface water transport water between these stores and generate a discontinuous normal component of flow. Thin objects in surface water with Kutta condition generates circulation by the discontinuous tangential component of flow across their interface. These discontinuities across hydrologic interfaces are quantified and visualized using the Analytic Element Method, where slit elements are formulated using the Joukowsky transformation with Laurent series and new influence functions to represent sinks and circulation, and methods are developed for these applications expressing discontinuities as Fourier series. The specific geometries illustrate solutions for a randomly generated heterogeneous porous media with non-intersecting inhomogeneities, for groundwater/surface water interaction in a synthetic river network, and for a slender body with geometry similar to the wings of the Wright Brothers. The mathematical details are reduced to series solutions and matrix multiplications, which are easily extensible to other geometries and applications. This article is protected by copyright. All rights reserved.
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  • 69
    Publication Date: 2015-09-25
    Description: Both flow field heterogeneity and mass transfer between mobile and immobile domains have been studied separately for explaining observed anomalous transport. Here, we investigate non-Fickian transport using high-resolution 3D X-ray micro-tomographic images of Berea sandstone containing microporous cement with pore size below the setup resolution. Transport is computed for a set of representative elementary volumes and results from advection and diffusion in the resolved macroporosity (mobile domain) and diffusion in the microporous phase (immobile domain) where the effective diffusion coefficient is calculated from the measured local porosity using a phenomenological model that includes a porosity threshold ( ɸ ϴ ) below which diffusion is null and the exponent n that characterizes tortuosity-porosity power-law relationship. We show that both flow field heterogeneity and microporosity trigger anomalous transport. Breakthrough curve (BTC) tailing is positively correlated to microporosity volume and mobile-immobile interface area. The sensitivity analysis showed that the BTC tailing increases with the value of ɸ ϴ , due to the increase of the diffusion path tortuosity until the volume of the microporosity becomes negligible. Furthermore, increasing the value of n leads to an increase in the standard deviation of the distribution of effective diffusion coefficients, which in turn results in an increase of the BTC tailing. Finally, we propose a continuous time random walk upscaled model where the transition time is the sum of independently distributed random variables characterized by specific distributions. It allows modeling a 1D equivalent macroscopic transport honoring both the control of the flow field heterogeneity and the multi-rate mass transfer between mobile and immobile domains. This article is protected by copyright. All rights reserved.
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  • 70
    Publication Date: 2015-09-29
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 71
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    Publication Date: 2015-09-29
    Description: The cover represents on opening window which represents the Novel Process Windows concept. Inside the window, a photomicroreactor can be seen. In photochemistry, photons are used to activate organic substrates for reactions. More information on the photomicroreactor design and its application can be found in the paper by Su et al. Yuanhai Su, Ali Talla, Volker Hessel, and Timothy Noël Controlled Photocatalytic Aerobic Oxidation of Thiols to Disulfides in an Energy-Efficient Photomicroreactor Chem. Eng. Technol. 2015 , 38 (10) , 1733–1742 DOI: 10.1002/ceat.201500376
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  • 72
    Publication Date: 2015-09-29
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 73
    Publication Date: 2015-09-29
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 74
    Publication Date: 2015-11-25
    Description: The optimization of installation of baffles in UV rector is investigated. The flow field is obtained by solving continuity equation and momentum equation. The radiation intensity is solved by use of radiative transfer equation. The UV dosage is obtained by coupling Lagrangian particle tracking approach with the solved radiation intensity. One unbaffled reactor and two baffled reactors are simulated. The baffled UV reactor A has the biggest residence time and the smallest UV dosage while the baffled UV reactor B has the relatively bigger residence time and the biggest UV dosage. The unbaffled reactor performs between two baffled reactors in residence time and UV dosage. The baffled UV reactor B can get the best disinfection of microorganisms. The present study shows that the optimization must be coupled the flow field and the radiation intensity to attain a harmony between them.
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  • 75
    Publication Date: 2015-11-24
    Description: Using airborne thermal infrared imaging and horizontally-resolved in situ temperature monitoring at the lake surface we estimated strength and duration of regular wind-driven upwelling of dense deep water to the lake surface in two small (in terms of Rossby radius) temperate lakes during the initial phase of summer thermal stratification. The onset and duration of the upwelling events correlated well with the balance between stratification (in terms of Schmidt Stability) and wind forcing, as expressed by Lake and Wedderburn Numbers: The period of regular upwelling appearances lasted 7-15 days, identified by Schmidt stabilities around 30 J m −2 and Lake Numbers between 0 and 1, and resulted in persistent temperature gradients of up to 2°C across the lake surface. Our results suggest that spring upwelling should inevitably take place in all freshwater temperate lakes with mean temperatures crossing the maximum density value of freshwater on annual cycle, whereas duration and intensity of the upwelling would vary depending on lake morphometry and weather conditions. Our results suggest major contribution of upwelling in nutrient supply to the upper waters, oxygenation of the deep water column, and air-lake gas exchange, in particular, the release of the sediment-produced methane into the atmosphere. This article is protected by copyright. All rights reserved.
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  • 76
    Publication Date: 2015-11-19
    Description: We provide a comprehensive experimental study of steady state, drainage relative permeability curves with CO 2 -brine and N 2 -deionised water, on a single Bentheimer sandstone core with a simple two-layer heterogeneity. We demonstrate that, if measured in the viscous limit, relative permeability is invariant with changing reservoir conditions, and is consistent with the continuum scale multiphase flow theory for water wet systems. Furthermore, we show that under capillary limited conditions, the CO 2 -brine system is very sensitive to heterogeneity in capillary pressure, and by performing core floods under capillary limited conditions, we produce effective relative permeability curves that are flow rate and fluid parameter dependent. We suggest that the major uncertainty in past observations of CO 2 -brine relative permeability curves is due to the interaction of CO 2 flow with pore space heterogeneity under capillary limited conditions and is not due to the effects of changing reservoir conditions. We show that the appropriate conditions for measuring intrinsic or effective relative permeability curves can be selected simply by scaling the driving force for flow by a quantification of capillary heterogeneity. Measuring one or two effective curves on a core with capillary heterogeneity that is representative of the reservoir will be sufficient for reservoir simulation This article is protected by copyright. All rights reserved.
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  • 77
    Publication Date: 2015-11-19
    Description: We examine the prediction capability of two approximate models (Multi Rate Mass Transfer, MRMT, and Continuous Time Random Walk, CTRW) of non-Fickian transport, by comparison with accurate 2D and 3D numerical simulations. Both non-local in time approaches circumvent the need to solve the flow and transport equations by using proxy models to advection, providing the breakthrough curves (BTC) at control planes at any x , depending on a vector of 5 unknown parameters. Although underlain by different mechanisms, the two models have an identical structure in the Laplace Transform domain and have the Markovian property of independent transitions. We show that also the numerical BTCs enjoy the Markovian property. Following the procedure recommended in the literature, along a practitioner perspective, we first calibrate the parameters values by a best fit with the numerical BTC at a control plane at x 1 , close to the injection plane, and subsequently use it for prediction at further control planes for a few values of . Due to a similar structure and Markovian property, the two methods perform equally well in matching the numerical BTC. The identified parameters are generally not unique, making their identification somewhat arbitrary. The inverse Gaussian model and the recently developed Multi Indicator model (MIM), which does not require any fitting as it relates the BTC to the permeability structure, are also discussed. The application of the proxy models for prediction requires carrying out transport field tests of large plumes for a long duration. This article is protected by copyright. All rights reserved.
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  • 78
    Publication Date: 2015-11-19
    Description: Virus removal during rapid transport in an unconfined, low-temperature (6°C) sand and gravel aquifer was investigated at a riverbank field site, 25 km south of Trondheim in central Norway. The data from bacteriophage MS2 inactivation and transport experiments were applied in a two-site kinetic transport model using HYDRUS-1D, to evaluate the mechanisms of virus removal and whether these mechanisms were sufficient to protect the groundwater supplies. The results demonstrated that inactivation was negligible to the overall removal, and that irreversible MS2 attachment to aquifer grains, coated with iron precipitates, played a dominant role in the removal of MS2; 4.1 log units of MS2 were removed by attachment during 38 m travel distance and less than 2 days residence time. Although the total removal was high, pathways capable of allowing virus migration at rapid velocities were present in the aquifer. The risk of rapid transport of viable viruses should be recognized, particularly for water supplies without permanent disinfection. This article is protected by copyright. All rights reserved.
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  • 79
    Publication Date: 2015-11-19
    Description: Upstream source control and Stormwater Treatment Areas (STAs) have reduced phosphorus (P) loads to Water Conservation Area 2A (WCA-2A), a northern Everglades wetland, by three-quarters since year 2000. Nevertheless, large storages of P remain in enriched peat soils and it is unclear how legacy stores will impact spatial and temporal scales of recovery. We re-measured soil P enrichment along a well-studied eutrophication gradient in WCA-2A and applied a profile modeling approach with uncertainty analysis to assess changes in longitudinal soil P gradients 13-years after load reductions. We then analyzed existing internal water P data, using a novel data screening approach, for evidence of lowest possible water P concentrations independent from inflows. We interpret such water P limits as evidence of the strength of internal loading at a location. Results indicate that soil P enrichment persists in the ∼7.5 km long “impacted” zone, with no significant evidence of net advancement or recession, while a large pool of labile P in the flocculent layer consolidated and diminished. There is indeed evidence, both spatial and temporal, that this extensive zone of enriched soil P continues to elevate lowest achievable water P concentrations. The corresponding gradient of elevated water P limits is both receding and diminishing since load reductions, thus providing further evidence toward recovery. However, results also suggest that these “transitory P limits” due to internal loading are likely to persist for decades above water quality targets. These results advance our understanding of recovery in impacted wetlands and are relevant to Everglades restoration. This article is protected by copyright. All rights reserved.
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  • 80
    Publication Date: 2015-11-19
    Description: Numerical modeling approaches with varying complexity were explored to investigate coupled groundwater flow and geochemical processes in saline basins. Long-term model simulations of a playa system gain insights into the complex feedback mechanisms between density driven flow and the spatio-temporal patterns of precipitating evaporites and evolving brines. Using a reactive multicomponent transport model approach the simulations reproduced, for the first time in a numerical study, the evaporite precipitation sequences frequently observed in saline basins (“bull's eyes”). Playa-specific flow, evapo-concentration and chemical divides were found to be the primary controls for the location of evaporites formed, and the resulting brine chemistry. Comparative simulations with the computationally far less demanding surrogate single-species transport models showed that these were still able to replicate the major flow patterns obtained by the more complex reactive transport simulations. However, the simulated degree of salinization was clearly lower than in reactive multicomponent transport simulations. For example, in the late stages of the simulations, when the brine becomes halite-saturated, the non-reactive simulation overestimated the solute mass by almost 20%. The simulations highlight the importance of the consideration of reactive transport processes for understanding and quantifying geochemical patterns, concentrations of individual dissolved solutes and evaporite evolution. This article is protected by copyright. All rights reserved.
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  • 81
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    Wiley
    Publication Date: 2015-11-21
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  • 82
    Publication Date: 2015-11-26
    Description: ABSTRACT A method is presented for using dissolved CFCs or SF 6 to estimate the apparent age of stream base flow by indirectly estimating the mean concentration of the tracer in the inflowing groundwater. The mean value is estimated simultaneously with the mean residence times of the gas and water in the stream by sampling the stream for one or both age tracers, along with dissolved nitrogen and argon at a single location over a period of approximately 12-14 hours. The data are fitted to an equation representing the temporal in-stream gas exchange as it responds to the diurnal temperature fluctuation. The efficacy of the method is demonstrated by collecting and analyzing samples at six different stream locations across parts of northern Virginia, USA. The studied streams drain watersheds with areas of between 2 and 122 km 2 during periods when the diurnal stream temperature ranged between 2 and 5°C. The method has the advantage of estimating the mean groundwater residence time of discharge from the watershed to the stream without the need for the collection of groundwater infiltrating to streambeds or local groundwater sampled from shallow observation wells near the stream. This article is protected by copyright. All rights reserved.
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  • 83
    Publication Date: 2015-11-26
    Description: ABSTRACT A between-groups experimental design examined public acceptance for managed aquifer recharge of stormwater for indirect potable and non-potable reuse; acceptance was based on five policy-related variables (fairness, effectiveness, trust, importance of safety assurances, and importance of communication activities). Results showed that public acceptance (N = 408) for managed aquifer recharge of stormwater was higher for non-potable applications, as was the importance of safety assurances. Analyses of variance also showed that perceptions of fairness and effectiveness were higher for a non-potable scheme, but not trust. A three-step hierarchical regression (Step 1: age, gender, education, income; Step 2: type of use; Step 3: fairness, effectiveness, trust, safety assurance, communication activities) demonstrated that type of stormwater use and the policy related factors accounted for 73% of the variance in acceptance of stormwater ( R 2 = .74, adjusted R 2 = .74, F (10, 397) = 113.919, p  〈 .001). Age, type of use and three of the five policy-related factors were also significant individual predictors of acceptance. The most important predictors were perceptions of trust in water authorities, perceptions of effectiveness, and perceptions of fairness. Interestingly, while safety assurance was important in attitudinal acceptance of managed aquifer recharge based on type of use, safety assurance was not found to be significant predictor of acceptance. This research suggests that policy-makers should look to address matters of greater public importance and drive such as fairness, trust and effectiveness of stormwater programs and advocate these at the forefront of their policies, rather than solely on education campaigns. This article is protected by copyright. All rights reserved.
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  • 84
    Publication Date: 2015-11-20
    Description: Observations at the field, catchment, and continental scales across a range of arid and semiarid climates and latitudes reveal aspect-controlled patterns in soil properties, vegetation types, ecohydrologic fluxes, and hillslope morphology. Although the global distribution of solar radiation on earth's surface and its implications on vegetation dynamics are well documented, we know little about how variation of solar radiation across latitudes influence landscape evolution and resulting geomorphic difference. Here, we used a landscape evolution model that couples the continuity equations for water, sediment, and aboveground vegetation biomass at each model element in order to explore the controls of latitude and mean annual precipitation (MAP) on the development of hillslope asymmetry (HA). In our model, asymmetric hillslopes emerged from the competition between soil creep and vegetation-modulated fluvial transport, driven by spatial distribution of solar radiation. Latitude was a primary driver of HA because of its effects on the global distribution of solar radiation. In the Northern Hemisphere, north-facing slopes (NFS), which support more vegetation cover and have lower transport efficiency, get steeper toward the North Pole while south-facing slopes (SFS) get gentler. In the Southern Hemisphere, the patterns are reversed and SFS get steeper towards the South Pole. For any given latitude, MAP is found to have minor control on HA. Our results underscore the potential influence of solar radiation as a global control on the development of asymmetric hillslopes in fluvial landscapes. This article is protected by copyright. All rights reserved.
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  • 85
    Publication Date: 2015-11-19
    Description: Temporal dynamics of sediment transport in steep channels using two experiments performed in a steep flume (8%) with natural sediment composed of 12 grain sizes are studied. High-resolution (1 sec) time series of sediment transport were measured for individual grain size classes at the outlet of the flume for different combinations of sediment input rates and flow discharges. Our aim in this paper is to quantify (a) the relation of discharge and sediment transport, and (b) the nature and strength of memory in grain-size dependent transport. None of the simple statistical descriptors of sediment transport (mean, extreme values, quantiles) display a clear relation with water discharge, in fact a large variability between discharge and sediment transport is observed. Instantaneous transport rates have probability density functions with heavy tails and bedload bursts have a coarser grain-size distribution than that of the entire experiment. We quantify the strength and nature of memory in sediment transport rates by estimating the Hurst exponent and the autocorrelation coefficient of the time series for different grain sizes. Our results show the presence of the Hurst phenomenon in transport rates, indicating long-term memory which is grain-size dependent. The short-term memory in coarse-grain transport increases with temporal aggregation and this reveals the importance of the sampling duration of bedload transport rates in natural streams, especially for large fractions. This article is protected by copyright. All rights reserved.
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  • 86
    Publication Date: 2015-11-19
    Description: In-channel structures are often installed in alluvial rivers during restoration to steer currents, but they also modify the streambed morphology and water surface profile, and alter hydraulic gradients driving ecologically important hyporheic exchange. Although river features before and after restoration need to be compared, few studies have collected detailed observations to facilitate this comparison. We created a laboratory mobile-bed alluvial meandering river and collected detailed measurements in the highly sinuous meander before and after installation of in-channel structures, which included one cross-vane and six J-hooks situated along one bar unit. Measurements of streambed and water surface elevation with sub-millimeter vertical accuracy and horizontal resolution were obtained using close-range photogrammetry. Compared to the smooth gradually varied water surface profile for control runs without structures, the structures created rapidly varied flow with sub- to super-critical flow transitions, as well as backwater and forced-morphology pools, which increased volumetric storage by 74% in the entire stream reach. The J-hooks, located along the outer bank of the meander bend and downstream of the cross-vane, created stepwise patterns in the streambed and water surface longitudinal profiles. The pooling of water behind the cross-vane increased the hydraulic gradient across the meander neck by 1% and increased local groundwater gradients by 4%, with smaller increases across other transects through the intra-meander zone. Scour pools developed downstream of the cross-vane and around the J-hooks situated near the meander apex. In-channel structures significantly changed meander bend hydraulic gradients, and the detailed streambed and water surface 3D maps provide valuable data for computational modeling of changes to hyporheic exchange. This article is protected by copyright. All rights reserved.
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  • 87
    Publication Date: 2015-11-19
    Description: Lakes are prevalent in the Arctic and thus play a key role in regional hydrology. Since many Arctic lakes are shallow and ice grows thick (historically 2-m or greater), seasonal ice commonly freezes to the lake bed (bedfast ice) by winter's end. Bedfast ice fundamentally alters lake energy balance and melt-out processes compared to deeper lakes that exceed the maximum ice thickness (floating ice) and maintain perennial liquid water below floating ice. Our analysis of lakes in northern Alaska indicated that ice-out of bedfast ice lakes occurred on average 17 days earlier (22-June) than ice-out on adjacent floating ice lakes (9-July). Earlier ice-free conditions in bedfast ice lakes caused higher open-water evaporation, 28% on average, relative to floating ice lakes and this divergence increased in lakes closer to the coast and in cooler summers. Water isotopes ( 18 O and 2 H) indicated similar differences in evaporation between these lake types. Our analysis suggests that ice regimes created by the combination of lake depth relative to ice thickness and associated ice-out timing currently cause a strong hydrologic divergence among Arctic lakes. Thus understanding the distribution and dynamics of lakes by ice regime is essential for predicting regional hydrology. An observed regime shift in lakes to floating ice conditions due to thinner ice growth may initially offset lake drying because of lower evaporative loss from this lake type. This potential negative feedback caused by winter processes occurs in spite of an overall projected increase in evapotranspiration as the Arctic climate warms. This article is protected by copyright. All rights reserved.
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  • 88
    Publication Date: 2015-11-23
    Description: A new method is proposed to produce three-dimensional facies models of braided-river aquifers based on analog data. The algorithm consists of two steps. The first step involves building the main geological units. The production of the principal inner structures of the aquifer is achieved by stacking Multiple-Point-Statistics simulations of successive topographies, thus mimicking the major successive flooding events responsible for the erosion and deposition of sediments. The second step of the algorithm consists of generating fine scale heterogeneity within the main geological units. These smaller-scale structures are generated by mimicking the trough-filling process occurring in braided rivers; the imitation of the physical processes relies on the local topography and on a local approximation of the flow. This produces realistic cross-stratified sediments, comparable to what can be observed in outcrops. The three main input parameters of the algorithm offer control over the proportions, the continuity and the dimensions of the deposits. Calibration of these parameters does not require invasive field measurements and can rely partly on analog data. This article is protected by copyright. All rights reserved.
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  • 89
    Publication Date: 2015-11-25
    Description: Stable isotope proving (SIP) enables function to be linked with identity without isolating the microorganisms responsible. This culture-independent approach has been adapted to identify the microorganisms involved in the degradation of numerous environmental contaminants. SIP studies have been performed in situ or in laboratory microcosms inoculated with soil, sediment, groundwater or bioreactor samples. This review focuses on the microorganisms that have been identified in those projects. SIP studies involving the degradation of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, gasoline associated contaminants, chlorinated solvents, RDX, phenol, uranium and pentachlorophenol are discussed. This review brings to light the significant diversity of contaminant degrading microorganisms.
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  • 90
    Publication Date: 2015-08-29
    Description: The problem of groundwater contamination in an aquifer is one with many uncertainties. Properly quantifying these uncertainties is essential in order to make reliable probabilistic based predictions and decisions regarding remediation strategies. In this work, a measure-theoretic framework is employed to quantify uncertainties in a simplified groundwater contamination transport model. Given uncertain data from observation wells, the stochastic inverse problem is solved numerically to obtain a probability measure on the space of unknown model parameters characterizing groundwater flow and contaminant transport in an aquifer, as well as unknown model boundary or source terms such as the contaminant source release into the environment. This probability measure is used to make predictions of future contaminant concentrations and to analyze possible remediation techniques. The ability to identify regions of small but nonzero probability using this method is illustrated. This article is protected by copyright. All rights reserved.
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  • 91
    Publication Date: 2015-08-29
    Description: Bayesian model averaging (BMA) ranks the plausibility of alternative conceptual models according to Bayes' theorem. A prior belief about each model's adequacy is updated to a posterior model probability based on the skill to reproduce observed data and on the principle of parsimony. The posterior model probabilities are then used as model weights for model ranking, selection, or averaging. Despite the statistically rigorous BMA procedure, model weights can become uncertain quantities due to measurement noise in the calibration data set or due to uncertainty in model input. Uncertain weights may in turn compromise the reliability of BMA results. We present a new statistical concept to investigate this weighting uncertainty, and thus to assess the significance of model weights and the confidence in model ranking. Our concept is to resample the uncertain input or output data, and then to analyze the induced variability in model weights. In the special case of weighting uncertainty due to measurement noise in the calibration data set, we interpret statistics of Bayesian model evidence to assess the distance of a model's performance from the theoretical upper limit. To illustrate our suggested approach, we investigate the reliability of soil-plant model selection following up on a study by Wöhling et al . [2015]. Results show that the BMA routine should be equipped with our suggested upgrade to (1) reveal the significant but otherwise undetected impact of measurement noise on model ranking results, and (2) to decide whether the considered set of models should be extended with better performing alternatives. This article is protected by copyright. All rights reserved.
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    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 92
    Publication Date: 2015-05-30
    Description: A continuous-flow microreactor was used to synthetize II–VI semiconductor quantum dots (CdSe). In order to improve the size distribution of the nanoparticles, the synthesis was carried out in a two-step procedure. A seed solution was obtained in a separate nucleation step, followed by a controllable growth step. Quantum dots that are synthesized with the two-step method show a much narrower size distribution in comparison to those obtained in a conventional batch synthesis. Quantum dots are nanocrystalline semiconductors that differ greatly from their bulk counterparts. To obtain CdSe quantum dots with a narrow size distribution, a two-step procedure was applied, in which CdSe seeds were synthesized in a separate process prior to the nanoparticle growing procedure. The seeds were mixed into the growing solution-containing droplet by coaxial injection.
    Print ISSN: 0930-7516
    Electronic ISSN: 1521-4125
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 93
    Publication Date: 2015-05-30
    Description: The chemical process industry is paying significant attention to the intensification of processes with the main aim of achieving increased productivity, improved economic status, and enhanced sustainability. The pharmaceutical industry is moving in the same direction and, therefore, dozens of processes are in a state of change. However, it is important to note that not all processes can be intensified easily, such as slow chemical reactions, processes with solids, slurries, and on the like. This review summarizes applications of promising tools for achieving process intensification in the small-scale pharmaceutical manufacturing of so-called small molecules. The focus is on microwave radiation, microreactors, ultrasounds, and meso-scale tubular reactors. Promising tools for accelerating slow chemical reactions in organic synthesis in order to achieve process intensification are reviewed with the focus on microwave radiation, meso-scale tubular reactors, microreactors, and ultrasounds. Applications of such tools for producing small molecules in the pharmaceutical industry are discussed and illustrated with examples.
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    Electronic ISSN: 1521-4125
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 94
    Publication Date: 2015-05-30
    Description: This study applies the image well theory in estimating the stream depletion rate (SDR) due to pumping near a meandering stream with a clogged streambed treated as the Robin condition. The stream is considered as an irregular boundary represented by discrete nodes. Image wells are arranged along the stream and near those nodes. On the basis of the Theis [1935] solution and the principle of superposition, the solution for the aquifer drawdown subject to the stream can then be expressed as the sum of the Theis solution and a simple series representing the effect of those image wells. The discharge rates of the image wells are determined by solving a system of equations obtained by substituting the drawdown solution into the Robin condition. Quantitative criteria for assessing the applicability of the image well theory are provided. On the basis of the drawdown solution and Darcy's law, the analytical solution for SDR can then be obtained. A finite element solution is also developed to verify the SDR solution. Temporal SDR distributions predicted by both the analytical solution and finite element solution agree well over the entire period except at late time when the stream filtration rate approaches the pumping rate (i.e., SDR≅1). It is found that a meandering stream has a significant effect on SDR compared with a rectilinear one and the effect should be taken into account in estimating SDR. This article is protected by copyright. All rights reserved.
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    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 95
    Publication Date: 2015-05-30
    Description: Observed streamflow of headwater catchments of the Tarim River (Central Asia) increased by about 30% over the period 1957–2004. This study aims at assessing to which extent these streamflow trends can be attributed to changes in air temperature or precipitation. The analysis includes a data-based approach using multiple linear regression, and a simulation-based approach using a hydrological model. The hydrological model considers changes in both glacier area and surface elevation. It was calibrated using a multiobjective optimization algorithm with calibration criteria based on glacier mass balance and daily and interannual variations of discharge. The individual contributions to the overall streamflow trends from changes in glacier geometry, temperature, and precipitation were assessed using simulation experiments with a constant glacier geometry, and with detrended temperature and precipitation time series. The results showed that the observed changes in streamflow were consistent with the changes in temperature and precipitation. In the Sari-Djaz catchment, increasing temperatures and related increase of glacier melt were identified as the dominant driver, while in the Kakshaal catchment, both increasing temperatures and increasing precipitation played a major role. Comparing the two approaches, an advantage of the simulation-based approach is the fact that it is based on process-based relationships implemented in the hydrological model instead of statistical links in the regression model. However, data-based approaches are less affected by model parameter and structural uncertainties and typically fast to apply. A complementary application of both approaches is recommended. This article is protected by copyright. All rights reserved.
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    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 96
    Publication Date: 2015-05-30
    Description: Despite their potential catastrophic impact, transients are often ignored or presented ad hoc when designing water distribution systems. To address this problem, we introduce a new piece-wise function fitting model that is integrated with mixed integer programming to optimally place and size surge tanks for transient control. The key features of the algorithm are a model-driven discretization of the search space, a linear approximation non-smooth system response surface to transients, and a mixed integer linear programming optimization. Results indicate that high quality solutions can be obtained within a reasonable number of function evaluations and demonstrate the computational effectiveness of the approach through two case studies. The work investigates one type of surge control devices (closed surge tank) for a specified set of transient events. The performance of the algorithm relies on the assumption that there exists a smooth relationship between the objective function and tank size. Results indicate the potential of the approach for the optimal surge control design in water systems. This article is protected by copyright. All rights reserved.
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    Topics: Architecture, Civil Engineering, Surveying , Geography
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  • 97
    Publication Date: 2015-05-30
    Description: In fluvial environments, feedbacks between flow, bedforms, sediment, and macrophytes results in a complex fluid dynamics. The assumptions underpinning standard tools in hydraulics are commonly violated and alternative approaches must be formulated. I argue that we should question the assumption that classical notions in fluid mechanics provide the foundations for the techniques of the future. Recent work on turbulent dissipation, interscale modulation of the dynamics, intermittency and the role of complex forcings is discussed. An agenda for future work is proposed that involves improving our characterization of complex forcings and developing better understanding of the behavior of the velocity gradient tensor in complex, fluvial environments. This leads to the formulation of modeling tools relevant to fluvial fluid mechanics, rather than a reliance on methods developed elsewhere. One avenue by which such methods might be developed is suggested based on the stretched spiral vortex as a baseline topology. This would result in a non-equilibrium model for turbulence that has greater potential to capture the dynamics in which we are interested. Although these ideas are raised in the context of a future fluvial fluid mechanics, they are applicable to any situation where turbulent flows are forced in complicated ways. This article is protected by copyright. All rights reserved.
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  • 98
    Publication Date: 2015-05-30
    Description: Although most freshwater resources are used in agriculture, residential water use is a much more energy intensive user. Based on this, we analyze the increased willingness to adopt water conservation strategies if energy cost is included in the customers' utility function. Using a Water-Energy-CO 2 emissions model for household water end uses and probability distribution functions for parameters affecting water and water-related energy use in 10 different locations in California, this research introduces a probabilistic two-stage optimization model considering technical and behavioral decision variables to obtain the most economical strategies to minimize household water and water-related energy bills and costs given both water and energy price shocks. Results can likely to be an upper bound of household savings for customers with well-behaved preferences, and show greater adoption rates to reduce energy intensive appliances when energy is accounted, resulting in an overall 24% reduction in indoor water use that represents a 30 percent reduction in water-related energy use and a 53 percent reduction in household water-related CO 2 emissions. Previous use patterns and water and energy rate structures can affect greatly the potential benefits for customers and so their behavior. Given that water and energy are somewhat complementary goods for customers, we use results of the optimization to obtain own-price and cross-price elasticities of residential water use by simulating increases in water and energy prices. While the results are highly influenced by assumptions due to lack of empirical data, the method presented has no precedent in the literature and hopefully will stimulate the collection of additional relevant data. This article is protected by copyright. All rights reserved.
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  • 99
    Publication Date: 2015-05-31
    Description: Fractures and defects in wellbore cement can lead to increased possibilities of CO 2 leakage from abandoned wells during geological carbon sequestration. To investigate the physicochemical response of defective wellbore cement to CO 2 -rich brine, we carried out a reactive flow-through experiment using an artificially fractured cement sample at a length of 224.8 mm. A brine solution with dissolved CO 2 at a pH of approximately 3.9 was injected through the sample at a constant rate of 0.0083 cm 3 /s. Surface optical profilometry analysis and 3D X-ray microtomography imaging confirmed fracture closure and self-healing behavior consistent with the measured permeability decrease. Visual inspection of the reacted fracture surface showed the development of reactive patterns mapping the flow velocity field inside the fracture, as well as restricted flow towards the sample outlet. The post-experiment permeability of the core sample was measured at half of its initial permeability. A reactive transport model was developed with parameters derived from the experiment to further examine property evolution of fractured cement under dynamic flow of CO 2 -rich brine. Sensitivity analysis showed that residence time and the size of initial fracture aperture are the key factors controlling the tendency to self-healing or fracture opening behavior and therefore determine the long-term integrity of the wellbore cement. Longer residence time and small apertures promote mineral precipitation, fracture closure, and therefore flow restriction. This work also suggests a narrow threshold separating the fracture opening and self-sealing behavior. This article is protected by copyright. All rights reserved.
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  • 100
    Publication Date: 2015-05-31
    Description: Precipitation quantile estimates are used in engineering, agriculture, and a variety of other disciplines. Index flood regional frequency methods pool normalized gauge data in the case of homogeneity among the constituent gauges of the region. Unitless regional quantile estimates are outputted and rescaled at each gauge. Because violation of the homogeneity hypothesis is a major component of quantile estimation error in regional frequency analysis, heterogeneity estimators should be “reasonable proxies” of the error of quantile estimation. In this study three Monte Carlo heterogeneity statistics tested in Hosking and Wallis [1997] are plotted against Monte Carlo estimates of quantile error for all five-or-more-gauge regionalizations in a twelve-gauge network in the Twin Cities region of Minnesota. Upper-tail quantiles with non-exceedance probabilities of 0.75 and above are examined at time-steps ranging from daily to monthly. A linear relationship between heterogeneity and error estimates is found and quantified using Pearson's r score. Two of Hosking and Wallis [1997]'s heterogeneity measures, incorporating the coefficient of variation in one case and additionally the skewness in the other, are found to be reasonable proxies for quantile error at the L-moment ratio values characterizing these data. This result, in addition to confirming the utility of a commonly used coefficient of variation-based heterogeneity statistic, provides evidence for the utility of a heterogeneity measure that incorporates skewness information. This article is protected by copyright. All rights reserved.
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