ALBERT

Description: The high elevation of the Southern Puna Plateau, the widespread melting of its crust, the gap in intermediate depth seismicity and the recent eruptions of ignimbrite complexes can be explained by delamination of the lithospheric mantle beneath it. To test this hypothesis, an array consisting of 73 broad band and short period seismic stations was deployed in the region for a period of two years starting in 2007. We inverted the data using the two plane wave approach and obtained 1D and 3D Rayleigh wave phase velocities. Our dispersion curve shows that at short periods (〈70 s) the phase velocities are slightly higher than those of the Tibetan plateau and lower than those of the Anatolian plateau. At periods of 100-140 s we observe a low velocity zone that might be remnant hot asthenosphere below a flat slab (7-10 Ma). We estimate the average continental lithosphere thickness for the region to be between 100 and 130 km. Our three dimensional Rayleigh wave phase velocities show a high velocity anomaly at low frequencies (0.007, 0.008 and 0.009 Hz) slightly to the north of Cerro Galan. This would be consistent with the hypothesis of delamination in which a piece of lithosphere has detached and caused upwelling of hot asthenosphere which in turn caused widespread alkaline-collision related volcanism. This interpretation is also corroborated by our shear wave velocity model where a high velocity anomaly beneath the northern edge of Cerro Galan at 130 km depth is interpreted as the delaminated block on top of the subducting Nazca slab.

Description: Homogenous liquid precursor for ZrC – SiC was prepared by blending of Zr ( OC 4 H 9 ) 4 and Poly[(methylsilylene)acetylene]. This precursor could be cured at 250°C and converted into binary ZrC – SiC composite ceramics upon heat treatment at 1700°C. The pyrolysis mechanism and optimal molar ratio of the precursor were investigated by XRD. The morphology and elements analyses were conducted by SEM and corresponding energy-dispersive spectrometer. The evolution of carbon during ceramization was studied by Raman spectroscopy. The results showed that the precursor samples heat treated at 900°C consisted of t- ZrO 2 (main phase) and m- ZrO 2 (minor phase). The higher temperature induced phase transformation and t- ZrO 2 converted into m- ZrO 2 . Further heating led to the formation of ZrC and SiC due to the carbothermal reduction, and the ceramic sample changed from compact to porous due to the generation of carbon oxides. With the increasing molar ratios of C / Zr , the residual oxides in 1700°C ceramic samples converted into ZrC and almost pure ZrC – SiC composite ceramics could be obtained in ZS-3 sample. The Zr , Si , and C elements were well distributed in the obtained ceramics powders and particles with a distribution of 100 ~ 300 nm consisted of well-crystallized ZrC and SiC phases.

Description: At present continental to global scale flood forecasting predicts at a point discharge, with little attention to detail and accuracy of local scale inundation predictions. Yet, inundation variables are of interest and all flood impacts are inherently local in nature. This paper proposes a large scale flood inundation ensemble forecasting model that uses best available data and modeling approaches in data scarce areas. The model was built for the Lower Zambezi River to demonstrate current flood inundation forecasting capabilities in large data-scarce regions. ECMWF ensemble forecast (ENS) data were used to force the VIC (Variable Infiltration Capacity) hydrological model, which simulated and routed daily flows to the input boundary locations of a 2-D hydrodynamic model. Efficient hydrodynamic modeling over large areas still requires model grid resolutions that are typically larger than the width of channels that play a key a role in flood wave propagation. We therefore employed a novel sub-grid channel scheme to describe the river network in detail whilst representing the floodplain at an appropriate scale. The modeling system was calibrated using channel water levels from satellite laser altimetry and then applied to predict the February 2007 Mozambique floods. Model evaluation showed that simulated flood edge cells were within a distance of between one and two model resolutions compared to an observed flood edge and inundation area agreement was on average 86%. Our study highlights that physically plausible parameter values and satisfactory performance can be achieved at spatial scales ranging from tens to several hundreds of thousands of km 2 and at model grid resolutions up to several km 2 .

Description: A class of capillary flows in unsaturated porous media is characterized by quasi-steady viscous flow confined behind curved air-water interfaces and within liquid bodies held by capillary forces along crevices and grain contacts. The geometry of the connected capillary liquid network within the pore space resembles channels that form between adjacent bubbles in foam (Plateau borders) with solid grains representing gas bubbles in foam. For simplified channel geometry we combine expressions for viscous flow with continuity considerations to describe the evolution of the channels cross-sectional area during gravity drainage. This formulation enables modeling of unsaturated flow without invoking the Richards equation and associated hydraulic functions. We adapt a formalism originally developed for foam “free drainage” (drainage under gravity) or “forced drainage” (infiltration front motion) to a class of unsaturated flows in porous media that require a few input parameters only (mean channel corner angle, air entry value and porosity) for certain initial and boundary conditions. We demonstrate that the reduction in capillary channel cross section yields a consistent description of self-regulating internal fluxes towards attainment of the so-called “field capacity” in soil and provides an alternative method for interpretation of outflow experiments for prescribed pressure boundary conditions. Additionally, the geometrically-explicit formulation provides a more intuitive picture of capillary flows across textural boundaries (changes in channel cross-section and number of channels). The foam drainage methodology expands the range of tools available for analyses of unsaturated flow processes and offers more realistic links between liquid configuration and flow dynamics in unsaturated porous media.

Description: Synthetic streamflows at different sites in a river basin are needed for planning, operation and management of water resources projects. Modeling the temporal and spatial dependence structure of monthly streamflow at different sites is generally required. In this study, the maximum entropy copula method is proposed for multisite monthly streamflow simulation, in which the temporal and spatial dependence structure is imposed as constraints to derive the maximum entropy copula. The monthly streamflows at different sites are then generated by sampling from the conditional distribution. A case study for the generation of monthly streamflow at three sites in the Colorado River basin illustrates the application of the proposed method. Simulated streamflow from the maximum entropy copula is in satisfactory agreement with observed streamflow.

Description: The Krycklan Catchment Study (KCS) provides a unique field infrastructure for hillslope to landscape-scale research on short and long-term ecosystem dynamics in boreal landscapes. The site is designed for process-based research assessing the role of external drivers including forest management, climate change, and long-range pollutant transport on forests, mires, soils, streams, lakes and groundwater. The over-arching objectives of KCS are to (1) provide a state-of-the-art infrastructure for experimental and hypothesis driven research, (2) maintain a collection of high quality, long-term climatic, biogeochemical, hydrological and environmental data, and (3) support the development of models and guidelines for research, policy and management.

Description: 3-D Hydraulic Tomography (3-D HT) is a method for aquifer characterization whereby the 3-D spatial distribution of aquifer flow parameters (primarily hydraulic conductivity, K) is estimated by joint inversion of head change data from multiple partially-penetrating pumping tests. While performance of 3-D HT has been studied extensively in numerical experiments, few field studies have demonstrated the real-world performance of 3-D HT. Here we report on a 3-D transient hydraulic tomography (3-D THT) field experiment at the Boise Hydrogeophysical Research Site which is different from prior approaches in that it represents a “baseline” analysis of 3-D THT performance using only a single arrangement of a central pumping well and 5 observation wells with nearly complete pumping and observation coverage at 1m intervals. We jointly analyze all pumping tests using a geostatistical approach based on the quasi-linear estimator of kitanidis [1995]. We reanalyze the system after progressively removing pumping and/or observation intervals; significant progressive loss of information about heterogeneity is quantified as reduced variance of the K field overall, reduced correlation with slug test K estimates at wells, and reduced ability to accurately predict independent pumping tests. We verify that imaging accuracy is strongly improved by pumping and observational densities comparable to the aquifer heterogeneity geostatistical correlation lengths. Discrepancies between K profiles at wells, as obtained from HT and slug tests, are greatest at the tops and bottoms of wells where HT observation coverage was lacking.

Description: Chlorine isotope compositions of high-pressure (~2.3 GPa) serpentinite, rodingite, and hydrothermally altered oceanic crust (AOC) differ significantly from high- and ultrahigh-pressure (〉3.2 GPa) metasedimentary rocks in the Aosta region, Italy. Texturally early serpentinites, rodingites, and AOC have bulk δ 37 Cl values indistinguishable from those of modern seafloor analogues (δ 37 Cl = -1.0 to +1.0‰). In contrast, serpentinites and AOC samples that recrystallized during exhumation have low δ 37 Cl values (-2.7 to -0.5‰); 37 Cl depletion correlates with progressive changes in bulk chemistry. HP/UHP metasediments have low δ 37 Cl values (median = -2.5‰) that differ statistically from modern marine sediments (median = -0.6‰). Cl in metasedimentary rocks is concentrated in texturally early minerals, indicating modification of seafloor compositions early in the subduction history. The data constrain fluid sources during both subduction- and exhumation-related phases of fluid-rock interaction: (1) Marine sediments at the top of the downgoing plate likely interacted with isotopically light pore fluids from the accretionary wedge in the early stages of subduction. (2) No pervasive interaction with externally derived fluid occurred during subsequent subduction to the maximum depths of burial. (3) Localized mixing between serpentinites and fluids released by previously isotopically modified metasediments occurred during exhumation in the subduction channel. Most samples, however, preserved protolith signatures during subduction to near-arc depths.

Description: We have measured Ni, Ca, and Mn in olivine phenocrysts from volcanoes in the Galápagos Archipelago to infer the mantle source lithologies. Results show that peridotite is the dominant source lithology for Fernandina, Floreana, Genovesa, Wolf Island, and Darwin Island. These volcanoes largely characterize the PLUME, WD, FLO and DUM Nd, Sr, and Pb isotopic endmembers of Harpp and White (2001). Volcan Wolf, Alcedo, Marchena, and Cerro Azul, also produced from the melting of peridotite sources, have isotopic compositions that can be defined by mixing of the 4 isotopic endmembers. Our analysis suggests that peridotite was present in the sources of the volcanoes covered in this study and therefore is the dominant source lithology of the Galápagos plume. Pyroxenite melting is generally focused in two isotopically distinct domains: Roca Redonda, Volcan Ecuador, and Sierra Negra in the enriched western part of the archipelago, and Santiago, Santa Cruz, and Santa Fe in the depleted east. One implication of this finding is that the Western and Eastern Pyroxenite Domains represent two separate bodies of recycled crust within the Galápagos mantle plume. Furthermore, both isotopically enriched and depleted domains of the archipelago were generated from mixtures of peridotite and pyroxenite. This suggests that there is no relationship between the source lithology of the Galápagos plume and its isotopic characteristics. The identification of peridotite source melting in volcanoes with isotopic characteristics that have been attributed to recycled crust points to the importance of mixing in OIB genesis, consistent with studies in the Canary Islands.

Description: Ce -doped BaTiO 3 -based ceramics were prepared and studied to satisfy ultra-broad temperature stability (from −55°C to 300°C, capacitance variation rate based on C 20°C is within ±15%). The sample with 0.6 mol% CeO 2 succeeds to achieve this performance with a remarkably high ceiling temperature of 300°C. Meanwhile, the sample has good dielectric and electrical properties at room temperature (ε r  = 1667, tanδ = 1.478%, ρ V  = 5.9 × 10 12  Ω·cm). Ce ion can substitute for Ti ion as Ce 4+ or Ba ion as Ce 3+ . The substitution decreases the spontaneous polarization of BaTiO 3 , and then weakens the ferroelectricity of BaTiO 3 . As a result, the temperature stability of samples is improved obviously. Besides, CeO 2 addition promotes the formation of exaggerated grains, which are consisting of Ba 6 Ti 17 O 40 .

Description: This study aims to optimize quantitative X-ray diffraction (XRD) mineralogical analysis of the minority phases in clinker. The proposed method consists of applying Rietveld quantitative refinement to the XRD patterns for both clinker and the insoluble residue remaining after it is attacked with methanol and salicylic acid (Takashima method). The method was tested with industrial clinker and the same material after modifying its mineralogy by refiring at 1500°C followed by slow cooling. The findings showed that the C 4 AF / C 3 A ratios for quickly and gradually cooled clinker were much higher when the clinker diffractograms were refined with the Rietveld procedure than when the proposed method was used. The proportion of C 3 A found with the proposed method was ≈2.8-fold higher than when Rietveld only was applied to the diffractograms for clinkers. Taken together, the refinement data for the two materials (clinker and Takashima residua) revealed that Rietveld quantitative XRD applied to clinker underestimates the low C 3 A content. These findings are supported by postsulfate attack durability studies conducted on cements prepared with the two clinkers.

Description: The effect of increasing poling fields on the properties of (1− x )BZT– x BCT compositions across the morphotropic phase boundary (MPB) is studied using large signal polarization and strain, small signal permittivity and piezoelectric coefficient, and XRD measurements. Successive poling causes charge carrier migration inducing an internal bias field, which becomes large with respect to the coercive field resulting in biased ferroelectric and ferroelastic switching. Improvements in piezoelectric coefficient of 9% are significantly smaller in the tetragonal 60BCT composition compared with the improvement of approximately 50% in the rhombohedral 40BCT and MPB 50BCT compositions. While the properties continue to change with increased poling fields, the remnant ferroelastic domain texture parallel to the field direction, as observed from XRD, stays approximately constant. The improvement in overall domain alignment leading to largely enhanced intrinsic piezoelectricity originates from the alignment of 180° domains and possibly non-180° domains in grains with orientations inclined to the electric field. As a result, poling is most effective in BZT–BCT materials that have low coercive fields, show low distortions and possess more polarization orientations, such as compositions in the rhombohedral phase field or near the MPB.

Description: The defect chemistry-modulated dielectric properties of dense yttria-doped zirconia ceramics prepared by conventional sintering (at 1350°C–1500°C) and electric field-assisted flash sintering (55 V/cm at 900°C) were studied by impedance spectroscopy. While the bulk dielectric properties from both sets of samples showed only small and insignificant changes in conductivity and permittivity, respectively, a huge increase of these properties was measured for the grain boundaries in the flash sintered specimens. A close analysis of these results suggests that flash sintering reduced grain-boundary thickness (by about 30%), while increasing the concentration of oxygen vacancies near these interfaces (by about 49%). The underlying mechanism proposed is electric field-assisted generation and accommodation of defects in the space-charge layers adjacent to the grain surface. The changes in measured permittivity are attributed to the boundary thickness effect on capacitance, while conductivity involved variations in its defect density-dependent intrinsic value, accounting for changes also observed in grain-boundary relaxation frequencies. Therefore, in terms of modifications to the specific dielectric properties of these materials, the overall consequence of flash sintering was to considerably lower the semi-blocking character of the grain boundaries.

Description: This article presents a detailed study on the nanoscaled interface between microelongated gold particles (GP) and biphase leucite/feldspar glass-ceramic matrix. The glass-ceramic composite with a nonuniform GP distribution was processed through hot-pressing under vacuum using a commercial dental ceramic furnace for glass-ceramic dental crown manufacturing. Heat treatments at 900°C, 1100°C, and 1300°C were conducted, and microstructural features along the interface were used to verify the chemical reactions between GP and glass-ceramic matrix. It was observed that the amorphous glass-ceramic matrix had nanoscaled biphase structures, and the distributed nanoscaled amorphous leucite phase was attracted to GP during hot-pressing, and was more reactive with GP than the feldspar phase. The thickness of the interfacial phase formed through chemical reactions between GP and glass-ceramic matrix is around 30 nm. The chemically bonded interface has contributed significantly toward the substantial improvements in both strength and toughness of the GP-reinforced glass-ceramic matrix composite. Characterization techniques, including X-ray diffraction and field-emission scanning electron Microscopy, incorporating X-ray microanalysis using energy dispersive spectrometry, have been employed in this study.

Description: Probabilistic estimates of future water levels and river discharge are usually simulated with hydrologic models using ensemble weather forecasts as main inputs. As hydrologic models are imperfect and the meteorological ensembles tend to be biased and underdispersed, the ensemble forecasts for river runoff typically are biased and underdispersed, too. Thus, in order to achieve both reliable and sharp predictions statistical post-processing is required. In this work Bayesian model averaging (BMA) is applied to statistically post-process ensemble runoff raw forecasts for a catchment in Switzerland, at lead-times ranging from 1 to 240 hours. The raw forecasts have been obtained using deterministic and ensemble forcing meteorological models with different forecast lead-time ranges. First, BMA is applied based on mixtures of univariate normal distributions, subject to the assumption of independence between distinct lead-times. Then, the independence assumption is relaxed in order to estimate multivariate runoff forecasts over the entire range of lead-times simultaneously, based on a BMA version that uses multivariate normal distributions. Since river runoff is a highly skewed variable, Box-Cox transformations are applied in order to achieve approximate normality. Both univariate and multivariate BMA approaches are able to generate well calibrated probabilistic forecasts that are considerably sharper than climatological forecasts. Additionally, multivariate BMA provides a promising approach for incorporating temporal dependencies into the post-processed forecasts. Its major advantage against univariate BMA is an increase in reliability when the forecast system is changing due to model availability.

Description: Paleomagnetic analysis and radiocarbon dating of an expanded Holocene deep-sea sediment sequence recovered by Integrated Ocean Drilling Program (IODP) Expedition 303 from Labrador Sea Site U1305 (Lat: 57°28.5 N, Long. 48°31.8 W, water depth 3459 m) provides insights into mechanisms that drive both paleomagnetic secular variation (PSV) and magnetization acquisition in deep-sea sediments. Seventeen radiocarbon dates on planktonic foraminifera define postglacial (c. 8 ka) sedimentation rates as ranging from 35 to 〉 90 cm/kyr. Alternating field (AF) demagnetization of u-channel samples show that these homogeneous sediments preserve a strong, stable, and consistently well-defined component magnetization. Normalized remanence records pass reliability criteria for relative paleointensity (RPI) estimates. Assuming that the age of magnetization is most accurately defined by well dated PSV records with the highest sedimentation rates, allows us to estimate and correct for temporal offsets at Site U1305 interpreted to result from post-depositional remanence acquisition at a depth of ~ 20 cm. Comparisons indicate that the northern North Atlantic PSV and RPI records are more consistent with European than North American records, and the evolution of virtual geomagnetic poles (VGP) are temporally and longitudinally similar to global reconstructions, though with much larger latitudinal variation. The largest deviations from a geocentric axial dipole (GAD) are observed during times of the highest intensities, in contrast to the usual assumption. These observations are consistent with the idea that PSV in the North Atlantic and elsewhere during the Holocene results from temporal oscillations of high latitude flux concentrations at a few recurrent locations.

Description: We derive a series solution for the nonlinear Boussinesq equation in terms of the similarity variable of the Boltzmann transformation in a semi-infinite domain. The first few coefficients of the series have been known for a long time, having been obtained by a truncated inversion of the series solution of the Blasius equation, but no direct recurrence relation was known for the complete series representing the solution of the Boussinesq equation. The series turns out to have a finite radius of convergence, which we estimate with a numerical complex-plane integration method that identifies the singularities of the solution when the equation is extended to the complex plane. The homogeneous condition at the origin produces a singularity which complicates numerical solutions with Runge-Kutta methods. We present two variable transformations that circumvent the problem and that are best suited to the complex-variable and the real-variable versions of the equation, respectively. Using those tools, an approximate solution accurate to 1.75 × 10 -10 and valid for the entire positive real axis is then developed by matching a Padé approximant of the exact series and an asymptotic solution (to overcome the restriction imposed by the finite radius of convergence of the series), along the same lines of the expression proposed by Hogarth and Parlange [1999]. The accuracies of all of the existing and the newly proposed solutions are obtained.

Description: Field sampling in unwadeable and flashy flood events encounters the problem that lateral variability of flow hydraulics and sediment transport cannot be captured adequately, and there is also an accuracy problem because parameters change while being measured. Moreover, event based gravel-sand mixed transport data in rapidly changing conditions are largely missing, in particular for gravel-bed rivers in small catchments. In this study, field measurements of bed load, suspended load, flow velocities, water depths and cross section geometry were collected during flood events at a monitoring station near the mouth of the Versilia river, Italy. Since the observed hydrographs are characterized by short durations, to the order of a few hours, an analysis of the lateral and temporal flow variability was carried out to enable the design of a sampling strategy and to minimize the errors created by the time variations of discharge associated with unsteady flow conditions. The measurements were interpreted using a 1D hydro-morphodynamic numerical model simulating the dynamics of flow and sediment discharges during a flood event for a given return period. The flow and sediment rating curves were then developed through an integrated approach combining different methodologies: field measurements, laboratory analyses and mathematical modeling. The developed approach allows one to capture the main physical mechanisms associated to the transport of sand–gravel mixtures, such as selective transport, and the hysteretic behaviour of sediment transport produced by rapid and intense flood events.

Description: Recent investigations have revealed the great potential of Raman spectroscopy for the characterization of clinker minerals and commercial Portland cements. The usefulness of this technique for the identification of anhydrous, hydrated, and carbonated phases in cement-based materials has been demonstrated. In the present work, the application of micro-Raman spectroscopy for the characterization of the main clinker phases of calcium aluminate cements and calcium sulfoaluminate cement is explored. The main stable hydrated phases as well as several important carbonated phases are investigated. Raman measurements on the following phases are reported: (i) pure, unhydrated phases: CA, C 12 A 7 , CA 2 , C 2 AS, cubic- C 3 A , C 4 AF, and C 4 A 3 ; (ii) hydrated phases: ettringite, monosulfoaluminate, and hydrogarnet ( C 3 AH 6 ); (iii) carboaluminate phases: hemicarboaluminate and monocarboaluminate. The present results, which are discussed in terms of the internal vibrational modes of the aluminate, carbonate, and sulfate molecular groups as well as stretching O–H vibrations, show the ability of Raman spectroscopy to identify the main hydrated and unhydrated phases in the aluminate and sulfoaluminate cements. The Raman spectra obtained in this work provide an extended database to the existing data published in the literature.

Description: Acmite ( NaFeSi 2 O 6 ) films were formed on steel coupons via solvothermal reaction of silica, sodium hydroxide, and 1, 4-butanediol in an autoclave under autogenous pressure. Systematic variation in processing variables led to homogenous coatings comprised of pinacoidal acmite grains with an average grain size of ~33 μm. The coatings were produced on the steel coupons from reactant conditions of 0.635 m SiO 2 , 2.546 m NaOH , and 3.087 m 1,4-butanediol for 72 h at 240°C.

Description: ABSTRACT A study was performed to characterize over land precipitation associated with tropical cyclones (TCs) for basins around the world based upon the International Best Track Archive for Climate Stewardship (IBTrACS). From 1998 to 2009, data from the Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis (TMPA) product 3B42, showed that TCs accounted for 5.5%, 7.5%, 6%, 9.5%, and 8.9% of the annual precipitation for impacted over land areas of the Americas, East Asia, South and West Asia, Oceania, and East Africa respectively, and that TC contribution decreased significantly within the first 150-km from the coast. Locally, TCs contributed on average to more than 25% and up to 61% of the annual precipitation budget over very different climatic areas with arid or tropical characteristics. East Asia represented the higher and most constant TC rain (118±19% mm y -1 ) normalized over the area impacted, while East Africa presented the highest variability (108±60% mm y -1 ), and the Americas displayed the lowest average TC rain (65±24% mm y -1 ) despite a higher TC activity. Furthermore, the maximum monthly TC contribution (8-11%) was found later in the TC season and depended on the peak of TC activity, TC rainfall, and the domain transition between dry and wet regimes if any. Finally, because of their importance in terms of rainfall amount, the contribution of TCs was provided for a selection of 50 urban areas experiencing cyclonic activity. Results showed that for particularly intense years, urban areas prone to cyclonic activity received more than half of their annual rainfall from TCs.

Description: A multivariate, multi-site daily weather generator is presented for use in decision-centric vulnerability assessments under climate change. The tool is envisioned useful for a wide range of socioeconomic and biophysical systems sensitive to different aspects of climate variability and change. The proposed stochastic model has several components, including 1) a wavelet decomposition coupled to an autoregressive model to account for structured, low-frequency climate oscillations, 2) a Markov Chain and k-nearest-neighbor (KNN) resampling scheme to simulate spatially-distributed, multivariate weather variables over a region, and 3) a quantile mapping procedure to enforce long-term distributional shifts in weather variables that result from prescribed climate changes. The Markov Chain is used to better represent wet and dry spell statistics while the KNN bootstrap resampler preserves the covariance structure between the weather variables and across space. The wavelet-based autoregressive model is applied to annual climate over the region and used to modulate the Markov Chain and KNN resampling, embedding appropriate low-frequency structure within the daily weather generation process. Parameters can be altered in any of the components of the proposed model to enable the generation of realistic time series of climate variables that exhibit changes to both lower-order and higher-order statistics at long-term (inter-annual), mid-term (seasonal), and short-term (daily) timescales. The tool can be coupled with impact models in a bottom-up risk assessment to efficiently and exhaustively explore the potential climate changes under which a system is most vulnerable. An application of the weather generator is presented for the Connecticut River basin to demonstrate the tool's ability to generate a wide range of possible climate sequences over an extensive spatial domain.

Description: The objective of the least cost design problem of a water distribution system is to find its minimum cost with discrete diameters as decision variables and hydraulic controls as constraints. The goal of a robust least cost design is to find solutions which guarantee its feasibility independent of the data (i.e., under model uncertainty). A robust counterpart approach for linear uncertain problems is adopted in this study, which represents the uncertain stochastic problem as its deterministic equivalent. Robustness is controlled by a single parameter providing a trade-off between the probability of constraint violation and the objective cost. Two principal models are developed-uncorrelated uncertainty model with implicit design reliability, and correlated uncertainty model with explicit design reliability. The models are tested on three example applications and compared for uncertainty in consumers’ demands. The main contribution of this study is the inclusion of the ability to explicitly account for different correlations between water distribution systems demand nodes. In particular it is shown that including correlation information in the design phase has a substantial advantage in seeking more efficient robust solutions.

Description: Moving from univariate to multivariate frequency analysis, this study extends the Klemeš' critique of the widespread belief that the increasingly refined mathematical structures of probability functions increase the accuracy and credibility of the extrapolated upper tails of the fitted distribution models. In particular, we discuss key aspects of multivariate frequency analysis applied to hydrological data such as the selection of multivariate design events (i.e., appropriate subsets or scenarios of multiplets that exhibit the same joint probability to be used in design applications) and the assessment of the corresponding uncertainty. Since these problems are often overlooked or treated separately, and sometimes confused, we attempt to clarify properties, advantages, shortcomings and reliability of results of frequency analysis. We suggest a selection method of multivariate design events with prescribed joint probability based on simple Monte Carlo simulations that accounts for the uncertainty affecting the inference results and the multivariate extreme quantiles. It is also shown that the exploration of the p -level probability regions of a joint distribution returns a set of events that is a subset of the p -level scenarios resulting from an appropriate assessment of the sampling uncertainty, thus tending to overlook more extreme and potentially dangerous events with the same (uncertain) joint probability. Moreover, a quantitative assessment of the uncertainty of multivariate quantiles is provided by introducing the concept of joint confidence intervals. From an operational point of view, the simulated event sets describing the distribution of the multivariate p -level quantiles can be used to perform multivariate risk analysis under sampling uncertainty. As an example of the practical implications of this study, we analyse two case studies already presented in the literature.

Description: Sparse geologic dictionaries provide a novel approach for subsurface flow model representation and calibration. Learning sparse dictionaries from prior training datasets is an effective approach to describe complex geologic connectivity patterns in subsurface imaging applications. However, the computational cost of sparse learning algorithms becomes prohibitive for large models. Performing the sparse dictionary learning process on smaller image patches (segments) provides a simple approach to address this problem in image processing applications. However, in underdetermined subsurface flow model calibration inverse problems, reconstruction of a segmented image can introduce significant structural distortion and discontinuity at the boundaries of the segments. This paper proposes an alternative sparse learning approach where the sparse dictionaries are learned from low-rank representations of the large-scale training dataset in spectral domains (e.g., frequency domain). The objective is to develop a computationally efficient dictionary learning approach that emphasizes large-scale spatial connectivity patterns. This is achieved by removing the strong spatial correlations in the training data, thereby eliminating a large number of insignificant components from the sparse learning computation. In addition to improving the computational complexity, sparse learning from low-rank training datasets suppresses the small-scale details from entering the reconstruction of large-scale connectivity patterns, and providing a regularization effect in solving the resulting ill-posed inverse problems. We apply the proposed approach to travel-time tomography inversion and nonlinear subsurface flow model calibration inverse problems to demonstrate its effectiveness and practicality.

Description: A 50:50 vol% MgO – Y 2 O 3 nanocomposite with ~150 nm grain size was prepared in an attempt to make 3–5 μm infrared-transmitting windows with increased durability and thermal shock resistance. Flexure strength of the composite at 21°C is 679 MPa for 0.88 cm 2 under load. Hardness is consistent with that of the constituents with similar grain size. For 3-mm-thick material at 4.85 μm, the total scatter loss is 1.5%, forward scatter is 0.2%, and absorptance is 1.8%. Optical scatter below 2 μm is 100%. Variable intensity OH absorption (~6% absorptance) is observed near 3 μm. The refractive index is ~0.4% below the volume-fraction-weighted average of those of the constituents. Thermal expansion is equal to the volume-fraction-weighted average of expansion of the constituents. Specific heat capacity is equal to the mass-fraction-weighted average of heat capacities of the constituents. Thermal conductivity lies between those of the constituents up to 1200 K. Elastic constants lie between those of the constituents. The Hasselman mild thermal shock resistance parameter for the composite is twice as great as that of common 3–5 μm window materials, but half as great as that of c -plane sapphire.

Description: The conditions permitting mantle serpentinization during continental rifting are explored within 2D thermotectonostratigraphic basin models, which track the rheological evolution of the continental crust, account for sediment blanketing effects, and allow for kinetically controlled mantle serpentinization processes. The basic idea is that the entire extending continental crust has to be brittle for crustal scale faulting and mantle serpentinization to occur [ Perez-Gussinye and Reston , 2001]. The isostatic and latent heat effects of the reaction are fully coupled to the structural and thermal solutions. A systematic parameter study shows that a critical stretching factor exists for which complete crustal embrittlement and serpentinization occurs. Increased sedimentation rates shift this critical stretching factor to higher values as sediment blanketing effects result in higher crustal temperatures. Sediment supply has therefore, through the temperature-dependence of the viscous flow laws, strong control on crustal strength and mantle serpentinization reactions are only likely when sedimentation rates are low and stretching factors high. In a case study for the Norwegian margin we test whether the inner lower crustal bodies (LCB) imaged beneath the Møre and Vøring margin could be serpentinized mantle. Multiple 2D transects have been reconstructed through the 3D data set by Scheck-Wenderoth and Maystrenko [2011]. We find that serpentinization reactions are possible and likely during the Jurassic rift phase. Predicted thicknesses and locations of partially serpentinized mantle rocks fit to information on LCBs from seismic and gravity data. We conclude that some of the inner LCBs beneath the Norwegian margin may be partially serpentinized mantle.

Description: A new hybrid wavelet–bootstrap–neural network (WBNN) model is proposed in this study for short term (1, 3 and 5 day; 1 and 2 week; and 1 and 2 month) urban water demand forecasting. The new method was tested using data from the city of Montreal in Canada. The performance of the WBNN method was compared with the autoregressive integrated moving average (ARIMA) and autoregressive integrated moving average model with exogenous input variables (ARIMAX), traditional NNs, wavelet analysis based NNs (WNN), bootstrap based NNs (BNN), and a simple naïve persistence index model. The WBNN model was developed as an ensemble of several NNs built using bootstrap resamples of wavelet sub-time series instead of raw datasets. The results demonstrated that the hybrid WBNN and WNN models produced significantly more accurate forecasting results than the traditional NN, BNN, ARIMA and ARIMAX models. It was also found that the WBNN model reduces the uncertainty associated with the forecasts, and the performance of WBNN forecasted confidence bands were found to be more accurate and reliable than BNN forecasted confidence bands. It was found in this study that maximum temperature and total precipitation improved the accuracy of water demand forecasts using wavelet analysis. The performance of WBNN models was also compared for different numbers of bootstrap resamples (i.e., 25, 50, 100, 200, and 500) and it was found that WBNN models produced optimum results with different numbers of bootstrap resamples for different lead time forecasts with considerable variability.

Description: In this work, novel Y 2 Si 2 O 7 / ZrO 2 composites were developed for structural and coating applications by taking advantage of their unique properties, such as good damage tolerance, tunable mechanical properties, and superior wear resistance. The γ- Y 2 Si 2 O 7 / ZrO 2 composites showed improved mechanical properties compared to the γ- Y 2 Si 2 O 7 matrix material, that is, the Young's modulus was enhanced from 155 to 188 GPa (121%) and the flexural strength from 135 to 254 MPa (181%); when the amount of ZrO 2 was increased from 0 to 50 vol%, the γ- Y 2 Si 2 O 7 / ZrO 2 composites also presented relatively high facture toughness (〉1.7 MPa·m 1/2 ), but this exhibited an inverse relationship with the ZrO 2 content. The composition–mechanical property–tribology relationships of the Y 2 Si 2 O 7 / ZrO 2 composites were elucidated. The wear resistance of the composites is not only influenced by the applied load, hardness, strength, toughness, and rigidity but also effectively depends on micromechanical stability properties of the microstructures. The easy growth of subcritical microcracks in Y 2 Si 2 O 7 grains and at grain boundaries significantly contributes to the macroscopic fracture toughness, but promotes the pull-out of individual grains, thus resulting in a lack of correlation between the wear rate and the macroscopic fracture toughness of the composites.

Description: ABSTRACT Although mechanistic reaction networks have been developed to quantify the biogeochemical evolution of subsurface systems associated with bioremediation, it is difficult in practice to quantify the onset and distribution of these transitions at the field scale using commonly collected wellbore datasets. As an alternative approach to the mechanistic methods, we develop a data-driven, statistical model to identify biogeochemical transitions using various time-lapse aqueous geochemical data (e.g., Fe(II), sulfate, sulfide, acetate, and uranium concentrations) and induced polarization (IP) data. We assume that the biogeochemical transitions can be classified as several dominant states that correspond to redox transitions and test the method at a uranium-contaminated site. The relationships between the geophysical observations and geochemical time-series vary depending upon the unknown underlying redox status, which is modeled as a hidden Markov random field. We estimate unknown parameters by maximizing the joint likelihood function using the maximization-expectation algorithm. The case study results show that when considered together aqueous geochemical data and IP imaginary conductivity provide a key diagnostic signature of biogeochemical stages. The developed method provides useful information for evaluating the effectiveness of bioremediation, such as the probability of being in specific redox stages following biostimulation where desirable pathways (e.g., uranium removal) are more highly favored. The use of geophysical data in the approach advances the possibility of using non-invasive methods to monitor critical biogeochemical system stages and transitions remotely and over field relevant scales (e.g., from square meters to several hectares).

Description: In recent years, a number of numerical modelling studies of transient sea-level rise (SLR) and seawater intrusion (SWI) in flux-controlled systems have reported an overshoot phenomenon, whereby the freshwater-saltwater interface temporarily extends further inland than the eventual steady-state position. In this study, we have carried out physical sand tank modelling of SLR-SWI in a flux-controlled unconfined aquifer setting to test if SWI overshoot is a measurable physical process. Photographs of the physical SLR experiments show, for the first time, that an overshoot occurs under controlled laboratory conditions. A sea-level drop (SLD) experiment was also carried out, and overshoot was again observed, whereby the interface was temporarily closer to the coast than the eventual steady-state position. This shows that an overshoot can occur for the case of a retreating interface. Numerical modelling corroborated the physical SLR and SLD experiments. The magnitude of the overshoot for SLR and SLD in the physical experiments was 24% of the change in steady-state interface position, albeit the laboratory setting is designed to maximise overshoot extent by adopting high groundwater flow gradients and large and rapid sea-level changes. While the likelihood of overshoot at the field scale appears to be low, this work has shown that it can be observed under controlled laboratory conditions.

Description: A new analytical solution of the flow equation has been developed to estimate the time to reach a near-equilibrium state in mixed aquifers, i.e. having unconfined and confined portions, following a large hydraulic perturbation. Near-equilibrium is defined as the time for an initial aquifer perturbation to dissipate by an average 95% across the aquifer.The new solution has been obtained by solving the flow system of a simplified conceptual model of a mixed aquifer using Laplace transforms. The conceptual model is based on two assumptions: 1) the groundwater flow can be reduced to a horizontal 1D problem; and 2) the transmissivity, a function of the saturated thickness, is assumed constant on the unconfined portion. This new solution depends on the storativity of the unconfined portion, the lengths of the unconfined and confined portions and the transmissivity, assumed to be constant and equal in both portions of the mixed aquifer. This solution was then tested and validated against a numerical flow model, where the variations of the saturated thickness and therefore variations of the transmissivity were either ignored, or properly modeled. The agreement between the results from the new solution and those from the numerical model is good, validating the use of this new solution to estimate the time to reach near-equilibrium in mixed aquifers. This solution for mixed aquifers, as well as the solutions for a fully confined or fully unconfined aquifer, have been used to estimate the time to reach near-equilibrium in thirteen large aquifers in the world. For those different aquifers, the time to reach near-equilibrium ranges between 0.7 ky to 2.4x10 7 ky. These results suggest that the present hydraulic heads in these aquifers are typically a mixture of responses induced from current and past hydrologic conditions and thus climate conditions. For some aquifers, the modern hydraulic heads may in fact depend upon hydrologic conditions resulting from several past climate cycles.

Description: The impact of contact angle on 2D spatial and temporal water content distribution during infiltration and drainage was experimentally studied. The 0.3-0.5 mm fraction of a quartz dune sand was treated and turned sub-critically repellent (contact angle of 33 0 , 48 0 , 56 0 , and 75 0 for S33, S48, S56, and S75, respectively). The media were packed uniformly in transparent flow chambers and water was supplied to the surface as a point source at different rates (1 to 20 ml/min). A sequence of grey-value images was taken by CCD camera during infiltration and subsequent drainage; grey values were converted to volumetric water content by water volume balance. Narrow and long plumes with water accumulation behind the downward moving wetting front (tip) and negative water gradient above it (tail) developed in the S56 and S75 media during infiltration at lower water application rates. The plumes became bulbous with spatially uniform water content distribution as water application rates increased. All plumes in these media propagated downward at a constant rate during infiltration and were frozen during drainage. In contrast, regular plume shapes were observed in the S33 and S48 media at all flow rates, and drainage profiles were non-monotonic with a transition plane at the depth that water reached during infiltration. Given that the studied media have similar pore-size distributions, the conclusion is that imbibition hindered by the non-zero contact angle induced pressure buildup at the wetting front (dynamic water entry value) that controlled the plume shape and internal water-content distribution during infiltration and drainage.

Description: The as-prepared BiFeO 3 ceramic shows a piezoelectric d 33 coefficient of −14 pC/N, that is, an obvious ferroelectric self-poling phenomenon. The temperature gradient between the two surfaces of BiFeO 3 ceramic was intentionally enlarged when BiFeO 3 was prepared with a rapid liquid sintering method. This temperature gradient and the corresponding thermal strain can introduce defect dipoles through separating bismuth vacancies from oxygen vacancies. A mass of these dipoles introduce a macroscopic internal electric field ( E in ) which downward poles BiFeO 3 ceramic during its cooling down process. As expected, an E in of 〉10 kV/cm is confirmed by the asymmetrical polarization/strain versus electric field curves.

Description: The effect of Ba content on the stress sensitivity of the antiferroelectric to ferroelectric phase transition in ( Pb 0.94− x La 0.04 Ba x )[( Zr 0.60 Sn 0.40 ) 0.84 Ti 0.16 ] O 3 ceramics is investigated through monitoring electric field-induced polarization and longitudinal strain under compressive prestresses. It is found that incorporation of Ba significantly suppresses the stress sensitivity of the phase transition, as manifested by slight decreases under prestresses up to 100 MPa in the maximum polarization ( P m ) and longitudinal strain ( x m ). The energy storage density is even increased under the mechanical confinement in compositions x  = 0.02 and 0.04. X-ray diffraction, transmission electron microscopy, and dielectric measurements indicate that the suppressed stress sensitivity is associated with the disruption of micrometersized antiferroelectric domains into nanodomains and the transition from antiferroelectric to relaxor behavior.

Description: Powders and nanoceramics composed of composites of CoFe 2 O 4 , CoFe 2 , and a small amount of FeO were prepared by heating CoFe 2 O 4 powder in reducing atmosphere and by sintering the product of reducing reaction at 350°C via spark plasma sintering technology. In the powders, increase in the molar ratios of CoFe 2 : CoFe 2 O 4 and a great change in magnetic parameters were observed with the change in heating temperature from 300°C to 400°C, and the dominance of dipole interaction over exchange coupling in the interparticle interactions was confirmed by the steps in magnetic hysteresis loops and the negative Henkel plots. However, in the nanoceramics, significant enhancement in exchange coupling was found when the sintering temperature was raised to 500°C and 650°C, which was confirmed by both the positivity of Henkel plot and the single-phase style of the magnetic hysteresis loop.

Description: Gas adsorption porosity measurement of geopolymers (GPs) is required for quantitative understanding of such mesoporous structures, but the complex nature of the GP system makes analysis difficult. Previous results in the literature are often ambiguous or contradictory. A systematic investigation of metakaolin GP gas adsorption results was conducted to optimize the use of this measurement technique and verify that results match known theory about GP structure. It was found that GP undergoes structural change upon degassing at 100°C or higher. If and only if this change is prevented by degassing at a lower temperature could it be shown that specific surface area and total gas adsorption increases with both increasing curing temperature and decreased Si : Al ratio. This observation is consistent with previous suggestions of increased zeolitic character under these conditions, where previous gas adsorption investigations had not observed this expected relationship. Hydrogen physisorption is proposed as a substitute technique for micropore isotherms in GPs due to the difficulty of removing trace gasses from GPs and the measurement effect of such gasses at high vacuum. A hydrogen physisorption isotherm qualitatively resembled an equivalent nitrogen micropore isotherm.

Description: Estimation of design quantiles of hydro-meteorological variables at critical locations in river basins is necessary for hydrological applications. To arrive at reliable estimates for locations (sites) where no or limited records are available, various regional frequency analysis (RFA) procedures have been developed over the past five decades. The most widely used procedure is based on Index-flood approach and L -moments. It assumes that values of scale and shape parameters of frequency distribution are identical across all the sites in a homogeneous region. In real world scenario, this assumption may not be valid even if a region is statistically homogeneous. To address this issue, a novel mathematical approach is proposed. It involves (i) identification of an appropriate frequency distribution to fit the random variable being analyzed for homogeneous region, (ii) use of a proposed transformation mechanism to map observations of the variable from original space to a dimensionless space where the form of distribution does not change, and variation in values of its parameters is minimal across sites, (iii) construction of a growth curve in the dimensionless space, and (iv) mapping the curve to the original space for the target site by applying inverse transformation to arrive at required quantile(s) for the site. Effectiveness of the proposed approach in predicting quantiles for ungauged sites is demonstrated through Monte-Carlo simulation experiments considering five frequency distributions that are widely used in RFA, and by case study on watersheds in conterminous United States. Results indicate that the proposed approach outperforms methods based on index-flood approach.

Description: Prediction of microbial surface water contamination is a formidable task because of the inherent randomness of environmental processes driving microbial fate and transport. In this article we develop a theoretical framework of a fully stochastic model of microbial transport in watersheds, and apply the theory to a simple flow network to demonstrate its use. The framework bridges the gap between microscopic behavior of individual microorganisms and macroscopic ensemble dynamics. This scaling is accomplished within a single mathematical framework, where each microorganism behaves according to a continuous-time discrete-space Markov process, and the Markov behavior of individual microbes gives rise to a non-homogeneous Poisson random field that describes microbial population dynamics. Mean value functions are derived, and the spatial and temporal distribution of water contamination risk is computed in a straightforward manner.

Description: In this work, the role of europium doping of glasses formulated in the ternary system ZnO – CdO – TeO 2 is described. The Eu -doped oxide glasses were prepared by the conventional melt-quenching method and by using three different compositions. Structural studies reveal that there exists a good affinity between Cd and some rare earth (RE) ions to form the crystalline phase. The X-ray diffraction (XRD) diagrams display that the structure of these glasses is amorphous and with the increase in CdO content and the compatibility of Eu 3+ , there is a tendency to form nanocrystals of CdTe 2 O 5 . The scanning electron microscopic (SEM) observation of their microstructure confirms the presence of phase separation. Differential thermal analysis (DTA) of these glasses showed small exothermic peaks noted around 450°C for the V2 glass and 480°C for V1 and V3 glasses, which could be attributed to the formation of these crystals. The infrared spectra showed a main absorption band around 800–600 cm −1 corresponding to the Te – O stretching mode in TeO 4 and TeO 3 groups. By optical absorption (OA), the band gap ( E g ) for each glass was determined; these values were 3.27, 3.14, and 3.3 eV for the V1–V3 glasses, respectively. Furthermore, the presence of Eu 3+ was detected in the 370–470 nm short-range wavelengths. The photoluminescence (PL) experiments of the glasses showed light emission due to the following transitions: 5D0 → 7F1, 5D0 → 7F2, 5D0 → 7F3, and 5D0 → 7F4.

Description: The conductivity of nominal CaWO 4 , CaW 0.99 Ta 0.01 O 4–δ , 0.7( CaWO 4 )–0.3( La 0.99 Ca 0.01 NbO 4–δ ), and Ca 0.9 La 0.1 WO 4+δ has been studied by means of a.c. impedance measurements. Proton conductivity was observed for CaW 0.99 Ta 0.01 O 4–δ , which displayed exothermic hydration with enthalpy and entropy of –82 kJ/mol and –120 J/molK, respectively. The proton mobility in CaW 0.99 Ta 0.01 O 4–δ was low, with enthalpy and preexponential factor of mobility of 82 kJ/mol and 0.7 cm 2 K/Vs. The high enthalpy of mobility is interpreted to reflect association between the acceptor dopant and protonic defects, whereas the low preexponential factor of mobility may reflect a lower proton concentration than assumed. Rietveld refinement indicated low solubilities of La on Ca -site and Ta on W-site. Proton conductivity was also observed in undoped CaWO 4 , however, not in Ca 0.9 La 0.1 WO 4+δ . The conductivity of 0.7( CaWO 4 )–0.3( La 0.99 Ca 0.01 NbO 4–δ ) behaved much like that of undoped LaNbO 4 , likely due to a very low acceptor dopant concentration.

Description: A new lead-free BNT-based piezoelectric ceramics of (1 −  x ) Bi 0.5 Na 0.5 TiO 3 – x Bi ( Al 0.5 Ga 0.5 ) O 3 ( x  = 0, 0.02, 0.03, 0.04, and 0.05) were synthesized using a conventional ceramic fabrication method. Their structures and electrical properties were investigated. All the samples show a typical ferroelectric P ( E ) loops and S ( E ) curves at room temperature. The optimal properties are obtained at the composition of the x  = 0.03. The substitution of Bi ( Al 0.5 Ga 0.5 ) O 3 enhances piezoelectric constant and increases Curie temperature from 58 pC/N and 310°C of pure BNT to 93 pC/N and 325°C of the x  = 0.03. The temperature-dependent P ( E ) loops and S ( E ) curves of 0.97BNT–0.03BAG indicate that phase transition from ferroelectric to antiferroelectric takes place over a very wide temperature region from 80°C to 180°C. The results show that the introduction of BAG improves the electrical properties of BNT.

Description: The origin of the Bermuda swell and volcanism remains enigmatic. The lack of an associated time-progressive hotspot track and absence of present-day volcanic activity make it difficult to reconcile with a deep mantle plume model. We analyze shear wave splitting measurements to estimate mantle flow direction and receiver function stacks to place constraints on the mantle transition zone thermal structure. *KS phases exhibit well-resolved null arrivals (no splitting) beneath the swell over a range of back azimuths. We find that the 410 and 660 km discontinuities are 49 ± 5 km and 19 ± 5 km deeper than the global average, respectively, leading to a transition zone thickness that is 27 ± 4 km thinner than average. Together, an apparently isotropic upper mantle and a thinned mantle transition zone suggest that mantle flow is primarily vertical beneath the swell, consistent with the presence of hot, buoyant mantle at depth.

Description: The anomalously snowy winter season of 2010/11 in the Sierra Nevada is analyzed in terms of snow water equivalent (SWE) anomalies and the role of atmospheric rivers (ARs)―narrow channels of enhanced meridional water vapor transport between the tropics and extratropics. Mean April 1 SWE was 0.44 m (56%) above normal averaged over 100 snow sensors. AR occurrence was anomalously high during the period, with 20 AR dates during the season and 14 in the month of December 2010, compared to the mean occurrence of 9 dates per season. Fifteen out of the 20 AR dates were associated with the negative phases of the Arctic Oscillation (AO) and the Pacific-North American (PNA) teleconnection pattern. Analysis of all winter ARs in California during water years 1998–2011 indicates more ARs occur during the negative phase of AO and PNA, with the increase between positive and negative phases being ˜90% for AO, and ˜50% for PNA. The circulation pattern associated with concurrent negative phases of AO and PNA, characterized by cyclonic anomalies centered northwest of California, provides a favorable dynamical condition for ARs. The analysis suggests that the massive Sierra Nevada snowpack during the 2010/11 winter season is primarily related to anomalously high frequency of ARs favored by the joint phasing of −AO and −PNA, and that a secondary contribution is from increased snow accumulation during these ARs favored by colder air temperatures associated with −AO, −PNA and La Niña.

Description: The baseflow recession constant, K b , is used to characterize the interaction of groundwater and surface water systems. Estimation of K b is critical in many studies including rainfall-runoff modeling, estimation of low flow statistics at ungaged locations and baseflow separation methods. The performance of several estimators of K b are compared, including several new approaches which account for the impact of human withdrawals. A traditional semi-log estimation approach adapted to incorporate the influence of human withdrawals was preferred over other derivative-based estimators. Human withdrawals are shown to have a significant impact on the estimation of baseflow recessions, even when withdrawals are relatively small. Regional regression models are developed to relate seasonal estimates of K b to physical, climatic, and anthropogenic characteristics of stream-aquifer systems. Among the factors considered for explaining the behavior of K b , both drainage density and human withdrawals have significant and similar explanatory power. We document the importance of incorporating human withdrawals into models of the baseflow recession response of a watershed and the systemic downward bias associated with estimates of K b obtained without consideration of human withdrawals.

Description: There are significant uncertainties inherent in precipitation forecasts and these uncertainties can be communicated to users via large ensembles that are generated using stochastic models of forecast error. The Met Office and the Australian Bureau of Meteorology developed the Short Term Ensemble Prediction System (STEPS) which has been operational for a number of years. The initial formulation of Bowler et al. [2006] has been revised and extended to improve the performance over large domains, to include radar observation errors, and to facilitate the combination of forecasts from a number of sources. This paper reviews the formulation of STEPS, discusses those aspects of the formulation that have proved most problematic and presents some solutions. The performance of STEPS nowcasts is evaluated using a combination of case study examples and statistical verification from the UK. Routine forecast verification demonstrates that STEPS is capable of producing near optimal blends of a rainfall nowcast and high resolution NWP forecast. It also shows that the spread of STEPS nowcast ensembles are a good predictor of the error in the control member (unperturbed) nowcast.

Description: In this study seasonal and interannual variability of the main atmospheric moisture sources over eight regions in the Mediterranean basin were investigated along a twenty one year period. The Lagrangian dispersion model FLEXPART, developed by Stohl and James [2004, 2005], was applied to identify the contribution of humidity to the moisture budget of each region. This methodology is used to compute budgets of evaporation minus precipitation (E-P) by calculating changes in the specific humidity along backward trajectories, for the preceding ten-day periods. The results show clear seasonal differences in the moisture sources between wet and dry seasons. The Western Mediterranean Sea is the dominant moisture source for almost all the regions in the Mediterranean basin during the wet season, while the local net evaporation dominates during the dry season. The highest interannual variability is found in contributions to the Iberian Peninsula, Italy and the Eastern Mediterranean. It is seen that the role of teleconnections is more limited than for the precipitation recorded in the region.

Description: We present a new hydrologic model based on the frequency distribution of hillslope landscape elements along the stream network as a basis for simulating landscape-scale hydrologic connectivity and catchment runoff. Hydrologic connectivity describes shallow water table continuity between upland and stream elements of the catchment and is important for the movement of water and solutes to streams. This concept has gained traction in physical hydrology but has received less attention in rainfall-runoff modeling. Our model is based on the empirical studies of Jencso et al. [2009; 2010], who found a strong correlation between the duration of shallow groundwater connectivity across hillslope, riparian, and stream zones and upslope accumulated area. We explored the relationship between catchment form and function by testing the extent to which streamflow generation could be predicted by a model based on the topographic form (distribution of landscape elements) of the catchment. We applied the model to the Stringer Creek catchment of the Tenderfoot Creek Experimental Forest, located in Montana, USA. Detailed field observations collected by Jencso et al. [2009] were used to inform the underpinnings of the model and to corroborate internal consistency of the model simulations. The model demonstrated good agreement between the observed and predicted streamflow and connectivity duration curves. The ability of this model to simulate internal dynamics without conditioning the parameters on these data suggests that it has the potential to be more confidently extrapolated to other shallow, topographically driven catchments than hydrologic models that fail to consistently reproduce internal variables.

Description: Knowledge of hydrological model complexity can aid selection of an optimal prediction model out of a set of available models. Optimal model selection is formalized as selection of the least complex model out of a subset of models that have lower empirical risk. This may be considered equivalent to minimizing an upper bound on prediction error, defined here as the mathematical expectation of empirical risk. In this paper we derive an upper bound that is free from assumptions on data and underlying process distribution as well as on independence of model predictions over time. We demonstrate that hydrological model complexity, as defined in the presented theoretical framework, plays an important role in determining the upper bound. The model complexity also acts as a stabilizer to a hydrological model selection problem if it is deemed ill-posed. We provide an algorithm for computing complexity of any arbitrary hydrological model. We also demonstrate that hydrological model complexity has a geometric interpretation as the size of model output space. The presented theory is applied to quantify complexities of two hydrological model structures: SAC-SMA and SIXPAR. It detects that SAC-SMA is indeed more complex than SIXPAR. We also develop an algorithm to estimate the upper bound on prediction error, which is applied on 5 different rainfall-runoff model structures that vary in complexity. We show that a model selection problem is stabilized by regularizing it with model complexity. Complexity regularized model selection yields models that are robust in predicting future but yet unseen data.

Description: The temporal dynamics and spatial distribution of the concentrations of dissolved gases (He, Ar, Kr, N 2 , O 2 and CO 2 ) in an infiltrating groundwater system fed by the peri-alpine River Thur (Switzerland) were analysed before, during and after a single, well-defined flood event. The analysis was based on measurements taken in five different groundwater observation wells that were located approximately 10 m apart and tapped the same groundwater body, but were situated in three different riparian zones. The input of O 2 into the groundwater as a result of the formation of excess air was found to be of the same order of magnitude as that resulting from the advection of river water, although the amount of excess air formed and the amount of O 2 delivered varied significantly among the riparian zones. The results suggest that the input of O 2 into groundwater as a result of excess air formation is controlled not only by the hydraulic conditions prevailing in the river and the groundwater, but also by the thickness of the confining bed at the top of the aquifer. The sandy gravel aquifer itself is too coarse to trap a significant amount of air during the water level rise. The clay layer confining the aquifer, however, acts as a barrier hindering the escape of air from the subsoil to the surface, and hence is likely to be a key factor controlling the trapping and dissolution of air in groundwater.

Description: Estimation of parameter values in hydrological models has gradually moved from subjective, trial-and-error methods into objective estimation methods. Translation of nature's complexity to bit operations is an uncertain process as a result of data errors, epistemic gaps, computational deficiencies, and other limitations, and relies on calibration to fit model output to observed data. The robustness of the calibrated parameter values to these types of uncertainties is therefore an important concern. In this study, we investigated how the hydrological robustness of the model-parameter values varied within the geometric structure of the behavioral (well-performing) parameter space with a depth function based on α shapes and an in-depth posterior performance analysis of the simulations in relation to the observed discharge uncertainty. The α shape depth is a non-convex measure that may provide an accurate and tight delimitation of the geometric structure of the behavioral space for both uni- and multimodal parameter-value distributions. WASMOD, a parsimonious rainfall-runoff model, was applied to six Honduran and one UK catchment, with differing data quality and hydrological characteristics. Model evaluation was done with two performance measures, the Nash-Sutcliffe efficiency and one based on flow-duration curves. Deep parameter vectors were in general found to be more hydrologically robust than shallow ones in the analyses we performed; model-performance values increased with depth, deviations to the observed data for the high-flow aspects of the hydrograph generally decreased with increasing depth, deep parameter vectors generally transferred in time with maintained high performance values, and the model had a low sensitivity to small changes in the parameter values. The tight delimitation of the behavioral space provided by the α shapes depth function showed a potential to improve the efficiency of calibration techniques that require further exploration. For computational reasons only a three-parameter model could be used, which limited the applicability of this depth measure and the conclusions drawn in this paper, especially concerning hydrological robustness at low flows.

Description: We present an improved density model and a new structural map of the Neapolitan Yellow Tuff caldera, the active portion of the nested Campi Flegrei caldera. The model was built using a new 3D inversion of the available high-precision gravity data, and a new digital terrain and marine model. The inversion procedure, based on a variable-depth lumped assembling of the subsurface gravity distribution via cell aggregation, gives better defined insights into the internal caldera architecture, that well agree with the available geological, geophysical and geochemical data. The adopted 3D gravity method is highly efficient for characterizing the shallow caldera structure (down to 3 km depth) and defining features related to regional or volcano tectonic lineaments and dynamics. In particular, the resulting density distribution highlights a pronounced density low in correspondence of the central portion of the caldera with a detail not available till now. The joint interpretation of the available data, suggests a subsurface structural setting that supports a piecemeal collapse of the caldera, and allows the identification of its headwall. Positive gravity anomalies localize dense intrusions (presently covered by late volcanic deposits) along the caldera marginal faults, and the main structural lineaments both bordering the resurgent block and cutting the caldera floor. These results allow us to both refine the current geological-structural framework and propose a new structural map that highlights the caldera boundary and its internal setting. This map is useful to interpret the phenomena occurring during unrest, and to improve both short- and long-term volcanic hazards assessment.

Description: Catastrophic collapses of submarine volcanoes have the potential to generate major tsunami, threatening many coastal populations. Recognizing the difficulties surrounding anticipations of these events, quantitative assessment of collapse-prone regions based on detailed morphological, geological and geophysical mapping can still provide important information about the hazards associated with these collapses. Rumble III is one of the shallowest, and largest, submarine volcanoes found along the Kermadec arc, and is both volcanically and hydrothermally active. Previous surveys have delineated major collapse features at Rumble III; based on time-lapse bathymetry, dramatic changes in the volcano morphology have been shown to have occurred over the interval 2007 to 2009. Furthermore, this volcano is located just ˜300 km from the east coast of the North Island of New Zealand. Here, we present a geophysical model for Rumble III, that provides the locations and sizes of potential weak regions of this volcano. Shipborne and near-seafloor geological and geophysical data collected by the AUV Sentry are used to determine the subsurface distribution of weak and unstable volcanic rocks. The resulting model provides evidence for potentially unstable areas located in the Southeastern flank of this volcano which should be included in future hazard predictions.

Description: Broadband seismic experiments over the last two decades have produced dense data coverage across Tibet. Yet, the mechanism of the India-Asia lithospheric convergence beneath it remains a puzzle, with even its basic features debated and with very different end-member models advocated today. We measured highly accurate Rayleigh- and Love-wave phase-velocity curves in broad period ranges (up to 5-200 s) for a few tens of pairs and groups of stations across Tibet, combining, in each case, hundreds to thousands of inter-station measurements made with cross-correlation and waveform-inversion methods. Robust shear-velocity profiles were then determined by extensive series of non-linear inversions of the data, designed to constrain the depth-dependent ranges of isotropic-average shear speeds and radial anisotropy. Temperature anomalies in the upper mantle were estimated from shear velocities using accurate petro-physical relationships. Our results reveal strong heterogeneity in the upper mantle beneath Tibet. Very large high-velocity anomalies in the upper mantle are consistent with the presence of underthrust (beneath southwestern Tibet) and subducted (beneath central and eastern Tibet) Indian lithosphere. The lithosphere. In contrast to the Indian lithosphere, Tibetan lithosphere and asthenosphere display low to normal shear speeds; Tibetan lithosphere is thus warm and thin. Radial anisotropy in the upper mantle is weak in central and strong in northeastern Tibet, possibly reflecting asthenospheric flow above the subducting Indian lithospheric slab.

Description: The Pacific Northwest (PNW) has experienced voluminous intraplate volcanism over the past ~17 Ma, beginning with the Steens/Columbia River flood basalts and continuing with the still-ongoing volcanism in the High Lava Plains (HLP) and eastern Snake River Plain (SRP). Here we present two complementary datasets (SKS splitting and Rayleigh wave phase velocity anisotropy) that place constraints on the anisotropic structure of the upper mantle beneath the HLP and SRP regions. Beneath the HLP, SKS phases reveal dominantly E-W fast splitting directions and large (up to ~2.7 sec) delay times, with pronounced lateral variations in δ t . Lateral and depth variability in the strength of anisotropy beneath the HLP is also evident from Rayleigh wave dispersion. Beneath the SRP, SKS splitting delay times are much smaller (~0.5 sec) and surface wave observations suggest a region of upper mantle anisotropy (~50-150 km depth) with a geometry that deviates significantly from the generally plate motion parallel fast directions observed just outside of the SRP. Beneath the HLP, the geometry of the anomalously strong anisotropy is similar to the anisotropy in the deeper parts of the upper mantle, resulting in constructive interference and large SKS splitting delay times. Beneath the SRP, the geometry of the anomalous anisotropic region in the shallow mantle is different, resulting in destructive interference and reduced SKS splitting delay times. We discuss several possible explanations for these observations, including variations in olivine lattice preferred orientation (LPO) strength, transitions in olivine fabric type, and a contribution from aligned partial melt.

Description: The cosmic-ray neutron probe measures soil moisture over tens of hectares, thus averaging spatially variable soil moisture fields. A previous paper described how variable soil moisture profiles affect the integrated cosmic-ray neutron signal from which depth-average soil moisture is computed. Here, we investigate the effect of horizontal heterogeneity on the relationship between neutron counts and average soil moisture. Observations from a distributed sensor network at a site in southern Arizona indicate that the horizontal component of the total variance of the soil moisture field is less variably in time than the vertical component. Using results from neutron particle transport simulations we show that 1-D binary distributions of soil moisture may affect both the mean and variance of neutron counts of a cosmic-ray neutron detector placed arbitrarily in a soil moisture field, potentially giving rise to an underestimate of the footprint average soil moisture. Similar simulations that used 1 and 2-D Gaussian soil moisture fields indicate consistent mean and variances of a randomly placed detector if the correlation length scales are short (〈˜30 m) and/or the soil moisture field variance is small (〈0.032 m 6 m -6 ). Taken together, these soil moisture observations and neutron transport simulations show that horizontal heterogeneity likely has a small effect on the relationship between mean neutron counts and average soil moisture for soils under natural conditions.

Description: We studied ancient enamels on gilded copper from a collection of archeological horse harness pendants of the Museo Instituto Valencia de Don Juan (Madrid, Spain) to test the benefits of a new, nondestructive analytical methodology based on chemometric analysis (i.e., Principal Component Analysis, PCA) on micro-ATR-FTIR spectral data and chemical quantification using SEM-EDS. The novelty of this approach was threefold: (i) PCA allowed the discrimination of the different harness pendants of known origin and attributed to the 14th and 15th centuries according to the chemical complex composition, nanostructure, glass weathering, and/or coloring mechanisms of each colored enamel, separately (i.e., red, purple, blue, and white), (ii) it is a cheap, easily available and nondestructive methodology that enables us to (iii) draw archeological conclusions about the quality of the manufacturing process, reassess the chronology of these objects and attempt to attribute them to different workshops according to the different traditional recipes identified. In particular, the enamels were made of alkali and/or alkaline earth lead-glass with a wide range of chemical compounds in the form of pigments or opacifiers. Two types of coloring mechanisms were identified, colloidal particles such as copper-ruby for red enamels, and ionic mechanisms such as Fe (II) and Co (II) to achieve a blue pigments; Mn (III) in the purple pigment; and two kind of white enamels were identified, i.e., tin oxide as an opacifier and uranium oxide. In addition, we established the reason for the poor state of conservation of some of the enamels by means of the identification of depolymerization and ion exchanges, well-known harmful effects of glass weathering, and finally a chronology was assigned for some of these pieces according to the enamel composition.

Description: Novel glass-ceramics with embedded thermoelectric Bi 2 Se 3 crystals were prepared from glass matrices in the Ge 20 Se 100− x Bi x ( x  = 5, 10, 12 mol%) system. Based on DSC results performed at different heating rates, characteristic activation energies ( E c ) and Avrami exponents ( n ) were obtained and analyzed by using Kissinger's relation, Ozawa's method, Augis–Bennett approximation and Matusita–Sakka theory. XRD results showed that pure Bi 2 Se 3 crystalline phase precipitated upon annealing at different temperatures for various time. The crystal size and crystalline fraction in the samples could be tuned by controlling the annealing time.

Description: In the present investigations nano size high alumina cements (HAC) were prepared by very effective co-melt precursor sintering technique from their metal nitrate precursors. The prime cementing phases observed were CA, CA 2 , and C 12 A 7 . The addition of nano structured cements in refractory castables has improved the thermo-chemical-mechanical properties to a significant extent. Each batch of low cement castables (LCC) was prepared from calcined Chinese bauxite, HAC, and superfine additives. The effect of HAC in bauxite castable with the additives similar to Silicon Carbide, reactive alumina, and micro-fine silica on the sinterability and properties of these castables was investigated. Physical properties such as apparent porosity and bulk density, mechanical properties such as hot modulus of rupture (HMOR), cold and hot modulus of rupture (CMOR), and cold crushing strength (CCS) of hydrated and sintered castables were studied. The sintered castables were also characterized for their solid phase compositions and microstructure using X-ray diffraction (XRD) and FE-SEM, respectively. In the castables new phases such as mullite, α-alumina were formed at the expense of bauxite and silica. Solid solution of mullite formed at high temperature acts as a bonding phase and is accounted for high HMOR, CMOR, and CCS values. These excellent properties of such castables may enable their uses in various applications such as refractory lining for fabrication of steel, aluminium, copper, glass, cement, chemicals, and ceramics.

Description: The bulk composition of the silicate portion of the Earth (BSE) has long been assumed to be tied to chondrites, in which refractory, lithophile elements like Sm and Nd exist in chondritic relative abundances. However, the 142 Nd/ 144 Nd ratios of modern terrestrial samples are 18±5 ppm higher than the ordinary-chondrite reservoir, and this challenges the traditional BSE model. Here we investigate a hypothesis that this terrestrial 142 Nd excess is related to a Sm/Nd ratio 6% higher than chondritic. This Sm/Nd ratio yields a superchondritic 143 Nd/ 144 Nd (~0.5130) similar to that identified in the highest 3 He/ 4 He mantle reservoir, and we argue that this reservoir represents the BSE composition for lithophile elements. We develop a compositional model for BSE in which the elevated Sm/Nd requires a shift of 143 Nd/ 144 Nd from 0.51263 (chondritic) to 0.51300. The new BSE composition is depleted in highly incompatible elements, including K, relative to the chondrite-based BSE, and offers a solution the “missing” 40 Ar paradox. This BSE compositional model requires that 〉83% of the mantle is depleted to form continental crust. It also implies a ~30% reduction in BSE U, Th and K, and therefore in the current rate of radiogenic heating and, thus, a proportional increase in the heat flow delivered to surface by plate tectonics. We explore thermal history models including effects related to a newly recognized evolution in the style of plate tectonics over Earth history: The lower radiogenic heat production may delay the onset of core convection and dynamo action to as late as 3.5 Gyr.

Description: The internal geological structure of the Northeast German Basin (NEGB) is affected by intense salt diapirism and by the presence of several stratified aquifer complexes of regional relevance. The shallow Quaternary to late Tertiary freshwater aquifer is separated from the underlying Mesozoic saline aquifers by an embedded Tertiary clay enriched aquitard (Rupelian Aquitard). An important feature of this aquitard is that hydraulic connections between the upper and lower aquifers do exist in areas where the Rupelian Aquitard is missing (hydrogeological windows). Three-dimensional thermohaline numerical simulations are carried out to investigate the effects of such hydrogeological windows in the Rupelian Aquitard on the resulting groundwater, temperature and salinity distributions. Numerical results suggest that hydrogeological windows act as preferential domains of hydraulic interconnectivity between the different aquifers at depth, and enable vigorous heat and mass transport which causes a mixing of warm and saline groundwater with cold and less saline groundwater within both aquifers. In areas where the Rupelian Aquitard confines the Mesozoic aquifer, dissolved solutes from major salt structures are transported laterally giving rise to plumes of variable salinity content ranging from few hundreds of meters to several tens of kilometers. Furthermore, destabilizing thermal buoyancy forces may overwhelm counteracting stabilizing salinity induced forces offside of salt domes. This may result in buoyant upward groundwater flow transporting heat and mass to shallower levels within the same Mesozoic Aquifer.

Description: Zn 2 GeO 4 ceramic materials were synthesized by the solid-state method. Zn 2 GeO 4 powders were investigated with X-ray powder diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Oxygen defects in the Zn 2 GeO 4 ceramics were investigated by photoluminescence, Raman, and EDS spectra. Conductivity of Zn 2 GeO 4 was 0.18 S/cm at low temperature of 773 K, and its activation energy was 0.49 eV. The results showed that Zn 2 GeO 4 was a promising low-temperature electrolyte with high conductivity.

Description: Widespread disturbance within forested catchments typically increases runoff. However, following widespread fire in 1939 throughout south-east Australia Kuczera [1987] reported persistent reductions in runoff that were attributed to increased evapotranspiration from regenerating ‘ash’ forests. Kuczera projected ongoing reductions of water yield for ~150 years. In 2003 widespread fire in the headwaters of the Murray-Darling Basin (MDB) again stimulated extensive regeneration of ash forests, raising the prospect of subsequent water yield reductions. To understand the potential impact of the 2003 bushfires we re-evaluated yield reductions from three of the catchments originally studied by Kuczera using the same calibration period. We also used an expanded pre-fire calibration period (1908-1938) based on data not originally available to Kuczera. The trend of post-fire water yield that we observed in 1939-affected catchments is qualitatively consistent with Kuczera's projections, but the quantitative details were, as expected, sensitive to the pre-fire calibration period used. We then used a simplified method to examine a further five ash-dominated catchments affected by the 2003 fires. We report relative reductions in mean annual stream flow in all five catchments and a statistically significant (α=0.05) post-fire reduction in one of five catchments. Post-fire yield reductions during the austral summer (October-April) were greater in relative magnitude in all five catchments and were statistically significant (α=0.05) in three of five catchments. We conclude that a post-bushfire Kuczera-type response may be widespread in regenerating ash forests. On that basis we anticipate post-fire yield reductions in ash forests elsewhere and conclude that further reductions in stream flow are likely in the MDB for at least another decade.

Description: Long continuous seismic data recorded at five broadband seismic stations during 2006 at Campi Flegrei caldera have been analyzed. Introducing a coarse-grained method, we evaluate the time evolution of amplitude and polarization of the seismic noise in the frequency band common to Long-Period events. The series are modulated on tidal time scales: the root-mean square is basically dominated by solar contribution, while the azimuth of the polarization vector shows lunar diurnal and semidiurnal constituents. In addition, we find that in the frequency band common to Long-Period events the azimuths are polarized towards a specific area, suggesting that these persistent oscillations can be induced by the activity of the shallow geothermal reservoir.

Description: We report on the mineralogical assemblages found in the hyper-alkaline springs hosted on Liguria and Oman ophiolites based on exhaustive XRD and SEM analyses. In Liguria, hyper-alkaline springs produce a thin brownish calcite precipitate that covers the bedrock due to the concomitant atmospheric CO 2 uptake and neutralization of the hyper-alkaline waters. No brucite and portlandite minerals are observed. The discharge of alkaline waters in Oman ophiolite forms white-orange precipitates. Calcium carbonate minerals (calcite and/or aragonite) are the most abundant and ubiquitous precipitates and are produced by the same mechanism as in Liguria. This process is observed as a thin surface crust made of rhombohedral calcite. Morphological features of aragonite vary from needle-, bouquet-, dumbbell-, spheroidal-like habitus according to the origin of carbon, the temperature and the ionic composition of the hyper-alkaline springs, and the biochemical and organic compounds. Brucite is observed both at hyper-alkaline springs located at the thrust plane and at the paleo-Moho. The varying mixing proportions between the surface run-off waters and the hyper-alkaline ones control brucite precipitation. The Layered Double Hydroxide minerals occur solely in vicinity of hyper-alkaline springs emerging within the bedded gabbros. Finally, the dominant mineralogical associations we found in Oman (Ca-bearing carbonates and brucite) in a serpentinizing environment driven by the meteoric waters are surprisingly the same as those observed at the Lost City hydrothermal site in a totally marine environment.

Description: This article details the influence of zirconium doping on the piezoelectric properties and relaxor characteristics of 94( Bi 1/2 Na 1/2 ) TiO 3 –6 Ba ( Zr x Ti 1− x ) O 3 (BNT–6BZT) bulk ceramics. Neutron diffraction measurements of BNT–6BZT doped with 0%–15% Zr revealed an electric-field-induced transition of the average crystal structure from pseudo-cubic to rhombohedral/tetragonal symmetries across the entire compositional range. The addition of Zr up to 10% stabilizes this transition, resulting in saturated polarization hysteresis loops with a maximum polarization of 40 μC/cm 2 at 5.5 kV/mm, while corresponding strain hysteresis measurements yield a maximum strain of 0.3%. With further Zr addition, the ferroelectric order is progressively destabilized and typical relaxor characteristics such as double peaks in the current density loops are observed. In the strain hysteresis, this destabilization leads to an increase of the maximum strain by 0.05%. These changes to the physical behavior caused by Zr addition are consistent with a reduction of the transition temperature T F-R , above which the field-induced transformation from the relaxor to ferroelectric state becomes reversible.

Description: Precursor glasses for the ferroelectric barium bismuth titanate ( BaBi 4 Ti 4 O 15 ) (BBiT) have been prepared by the melt-quench technique in the SiO 2 – K 2 O – BaO – Bi 2 O 3 – TiO 2 (SKBBT) glass system with and without Eu 2 O 3 doping. BBiT glass–ceramic (GC) nanocomposites have been derived from these glasses by controlled heat treatment. The structural properties of the GCs have been investigated using X-ray diffraction (XRD), electron microscopy (FE-SEM, TEM), and FT-IR reflectance spectroscopy. FE-SEM images show the formation of randomly oriented hexagonal rod-shaped crystals of 200–400 nm and TEM images show 10–20 nm crystallites. FT-IR spectra exhibit the characteristic bands of BBiT at 480, 585, and 680 cm −1 . The activation energy of crystallization ( E c ) varies from 295 to 307 kJ/mol. The dielectric constants (ε r ) of glass and GC nanocomposites increase with an increase in frequency up to 3.0 MHz and then decrease up to 5.0 MHz. Heat-treated GCs show higher ε r values, in the range 25–55, compared to the precursor glasses (20–37). Dielectric losses (tan δ) for all the samples increase from 0.005 to 1.0 with an increase in frequency from 100 Hz to 5.0 MHz. Excitation spectra were recorded by monitoring emission at 613 nm corresponding to the 5 D 0 → 7 F 2 transition. An intense 466 nm excitation band corresponding to the 7 F 0 → 5 D 2 transition was observed. Emission spectra were then recorded by exciting the glass samples at 466 nm. Longer heat-treatment times led to a 15-fold increase in the intensity of the red emission at 612 nm, attributed to the segregation of Eu 3+ ions into the low phonon energy BBiT crystallites. The hardness (3.8–5.1 GPa) and fracture toughness (1.8–3.5 MPam 0.5 ) values obtained in the GCs are high and suitable for structural applications.

Description: Carbon doping is known to be very effective for enhancing the high-field properties of magnesium diboride, MgB 2 , but not for the low-field properties. Here, we report that both the high- and the low-field properties can be improved simultaneously without doping by increasing the initial magnesium partial pressure, by simply reducing the size of the magnesium particles. It is shown that in situ processed bulk MgB 2 sintered with fine magnesium powders has superior superconducting properties compared with a bulk sample fabricated using coarse magnesium lumps. The change in the lattice parameters was almost negligible; however, a clear increase in lattice strain can be observed for the sample sintered with fine magnesium powders. The increase in the lattice strain results in an enhancement of the high-field properties. Furthermore, it has also been found that the low-field critical current density is not reduced, but rather slightly increased for the fine magnesium powder sample. This is due to a closer linkage among the grains that drastically improves grain connectivity. These findings demonstrate that the initial growth mechanism of MgB 2 is very crucial for its superior superconducting properties, and it especially indicates the importance of magnesium vapor pressure.

Description: Revisiting classic phase diagrams and chemical phase relations in the solid state of a very well-studied oxide system, such as the lithium aluminosilicate (LAS) system, can open a new window for the design of new advanced materials with improved properties. Crystal chemistry and phase equilibria are used to demonstrate the ability to design materials with particular desired properties in the alumina-rich corner of the LAS phase diagram. The experimental results demonstrate the alumina and β-eucryptite solid-state compatibility.

Description: This work reports the crystallization, microstructure, and surface composition of Cu In 0.7 Ga 0.3 Se 2 (CIGS) thin films grown by femtosecond pulsed laser deposition at different annealing temperatures. The structural and optical properties of the CIGS films were characterized by X-ray diffraction, Raman scattering, UV-visible spectroscopy, and Hall effect measurement. The results indicate that binary crystals of CuS e initially formed on the as-deposited film, but then completely turned into a quaternary chalcopyrite structure after annealing at 400°C. Phase transformation significantly affects the surface morphology, Hall properties, and band gap. Transmission electron microscopy further revealed that an interface between the Mo substrate and CIGS crystallites contains an amorphous layer even at the high temperature of 500°C. For the application of photovoltaic devices, we also report on the photoresponse of both as-deposited and annealed films as demonstrated by preliminary tests.

Description: Reactive sintering of 3 Ti : Sn :2 C and 3Ti:Sn:2C:0.6Fe powder mixtures is studied in the temperature range 510°C–1200°C under argon. It is demonstrated that the recently discovered Ti 3 SnC 2 phase is formed, provided that Fe is added to a 3 Ti : Sn :2 C reactant mixture within the synthesis conditions used. Using dilatometric and X-Ray diffraction analyses, the formation mechanism of Ti 3 SnC 2 is discussed. Results show that at low temperature (about 510°C), tin is consumed to form Fe x Sn y intermetallics. At high temperature (about 1060°C), tin is newly available to form Ti 3 SnC 2 due to the melting of Fe x Sn y . Then, the intermediate phases, TiC and Ti 2 SnC , and/or Ti 5 Sn 3 , TiC , C , and Ti are dissolved in the ( Fe  +  Sn ) liquid phase and Ti 3 SnC 2 very likely precipitate from the melt. The second part of the study deals with the optimization of the Fe content in the initial 3Ti:Sn:2C reactant powder mixture to synthesize samples with larger Ti 3 SnC 2 content by hot isostatic pressing.

Description: The effects of non-stoichiometry on the microstructure, oxygen vacancies, and piezoelectric properties of ( Na 0.5 K 0.5 ) x NbO 3 (NK x N, where x  =   0.98, 1.00, 1.01, and 1.02) ceramics doped with sintering aid CuTa 2 O 6 (CT) doping were investigated. X-ray diffraction (XRD) patterns indicated that a secondary phase formed in CT-doped NK x N (NK x NCT) ceramics with x  〈   1.00 and that a pure phase was obtained with x  ≥   1.00. The grain size of NK x NCT ceramics increased with increasing x value due to the formation of a liquid phase. The internal bias field, activation energy, and Raman analysis for NK x NCT ceramics showed that the number of induced oxygen vacancies increased with decreasing x value. The high mechanical quality factor ( Q m ) value obtained for NK x NCT ceramics did not correspond to a higher concentration of oxygen vacancies, illustrating that the suitable compensation (excess Na and K ) is more important than the concentration of oxygen vacancies to obtain the ceramics with high Q m values. The NK x NCT ceramics with x  =   1.01 exhibited excellent piezoelectric properties, with k p and Q m values of 39.9% and 2,070, respectively.

Description: Low-temperature sintering of β-spodumene ceramics with low coefficient of thermal expansion (CTE) was attained using Li 2 O – GeO 2 sintering additive. Single-phase β-spodumene ceramics could be synthesized by heat treatment at 1000°C using highly pure and fine amorphous silica, α-alumina, and lithium carbonate powders mixture via the solid-state reaction route. The mixture was calcined at 950°C, finely pulverized, compacted, and finally sintered with or without the sintering additive at 800°C–1400°C for 2 h. The relative density reached 98% for the sample sintered with 3 mass% Li 2 O – GeO 2 additive at 1000°C. Its Young's modulus was 167 GPa and flexural strength was 115 MPa. Its CTE (from R.T. to 800°C) was 0.7 × 10 −6  K −1 and dielectric constant was 6.8 with loss tangent of 0.9% at 5 MHz. These properties were excellent or comparative compared with those previously reported for the samples sintered at around 1300°C–1400°C via melt-quenching routes. As a result, β-spodumene ceramics with single phase and sufficient properties were obtained at about 300°C lower sintering temperature by adding Li 2 O – GeO 2 sintering additive via the conventional solid-state reaction route. These results suggest that β-spodumene ceramics sintered with Li 2 O – GeO 2 sintering additive has a potential use as LTCC for multichip modules.

Description: Pyrochlore-structured lanthanide stannate ceramic ( Ln 2 Sn 2 O 7 ) has been synthesized via a new complex precipitation method. A suite of characterization techniques, including FTIR, Raman, X-ray, and electron diffraction as well as nitrogen sorption were employed to investigate the structural evolution of the synthesized and calcined powder. Raman, XRD, and selected area electron diffraction results confirm the presence of the pyrochlore structure after calcination of the powder above 1200°C. TEM imaging shows fine crystallites gradually increased in size from approximately 100 nm to about 500 nm with higher calcination temperatures. Grain growth and powder densification upon increasing the calcination temperature was confirmed by nitrogen sorption results. This aqueous synthetic method provides a simple pathway for the preparation of homogeneous lanthanide stannate ceramics.

Description: A computer program (PBUQ) that uses Monte Carlo simulations to propagate uncertainty through regression equations and the equation for the paleosol carbonate CO 2 paleobarometer is presented. PBUQ includes options for all of the common approaches to determining values for input variables and incorporates several recent advancements relevant to determining values for soil-respired CO 2 concentrations, δ 13 C values of respired CO 2 , δ 13 C values of atmospheric CO 2 and temperatures of soil carbonate formation. PBUQ is intended to improve confidence in paleoatmospheric CO 2 research by helping researchers draw statistically significant conclusions. PBUQ can also be used to attribute and partition error among various sources and thereby advance this technique. Sensitivity analysis indicates that S(z) is the largest source of uncertainty for most paleosols and that uncertainty is minimized for soils in which CO 2 is an evenly balanced mixture between soil-derived and atmospheric components. Evenly balanced mixtures are most likely for paleosols formed in deserts and for weakly-developed paleosols. Development of proxies for soil-respired CO 2 concentrations and δ 13 C values of soil-respired CO 2 specifically for such soils is perhaps the most crucial next step for improving this technique. Currently, calcic paleosols are best used to test the significance of trends and/or differences among time slices in paleoatmospheric CO 2 concentration. Application to quantifying Earth System Sensitivity will require large scale averaging of determinations from individual paleosols and/or reduced uncertainty associated with input variables.

Description: Long-lived detachment faults are now known to be important in tectonic evolution of slow-spreading mid-ocean ridges, and there is increasing evidence that fluid flow plays a critical role in development of detachment systems. Here we document a new manifestation of low-temperature hydrothermal venting associated with the detachment fault that formed Kane Megamullion ~3.3-2.1 m.y. ago in the western rift-valley wall of the Mid-Atlantic Ridge. Hydrothermal effects on the detachment surface include 1) cemented mounds of igneous rock and chalk debris containing hydrothermal Mn oxides and Fe oxyhydroxides, and 2) layered deposits of similar Fe-Mn minerals ± interbedded chalks. Mounds are roughly conical, ~1-10 meters high, and contain primarily basalts with lesser gabbro, serpentinite, and polymict breccia. The layered Fe-Mn-rich sediments are flat-bedded to contorted and locally are buckled into low-relief linear or polygonal ridges. We propose that the mounds formed where hydrothermal fluids discharged through the detachment hanging wall near the active fault trace. Hydrothermal precipitates cemented hanging-wall debris and welded it to the footwall, and this debris persisted as mounds as the footwall was exhumed and surrounding unconsolidated material sloughed off the sloping detachment surface. Some of the layered Fe-Mn-rich deposits may have precipitated from fluids discharging from the hanging-wall vents, but they also precipitated from low-temperature fluids venting from the exposed footwall through overlying chalks. Observed natural disturbance and abnormally thin hydrogenous Fe-Mn crusts on some contorted, hydrothermal Fe-Mn-rich chalks on ~2.7 Ma crust suggest diffuse venting that is geologically recent. Results of this study imply that there are significant fluid pathways through all parts of detachment systems and that low-temperature venting through fractured detachment footwalls may continue for several million years off-axis.

Description: Drought triggers are patterns in hydro-climatic variables that herald upcoming droughts and form the basis for mitigation plans. This study develops a new method for identification of triggers for hydrologic droughts by examining the association between the various hydro-climatic variables and streamflows. Since numerous variables influence streamflows to varying degrees, Principal Component Analysis (PCA) is utilized for dimensionality reduction in predictor hydro-climatic variables. The joint dependence between the first two principal components, that explain over 98% of the variability in the predictor set, and streamflows is computed by a scale-free measure of association using asymmetric Archimedean copulas over two study watersheds in Indiana, USA, with unregulated streamflows. The M6 copula model is found to be suitable for the data and is utilized to find expected values and ranges of predictor hydro-climatic variables for different streamflow quantiles. This information is utilized to develop drought triggers for one-month lead time over the study areas. For the two study watersheds, soil moisture, precipitation and runoff are found to provide the fidelity to resolve amongst different drought classes. Combining the strengths of PCA for dimensionality reduction and copulas for building joint dependence allows the development of hydrologic drought triggers in an efficient manner.

Description: We present a unified asymptotic theory of rainfall extremes including annual maxima, excesses above high thresholds, and intensity-duration-frequency (IDF) curves that builds on previous findings and derive new non-asymptotic results. The analysis is based on stationary multifractal representations of rainfall and produces extensions of the familiar results from extreme value (EV) and extreme excess (EE) theories. The latter results apply to the T -yr maximum as and the excess above z as . By exploiting the scaling relationship among the distributions of rainfall intensity for different averaging durations d , the multifractal asymptotics include, in addition, results in the small-scale limits and with α 〉 0. In all cases the maximum distributions are of the generalized extreme value (GEV) type, but the index k depends on the limit considered. Multifractal models produce also asymptotic scaling results for the IDF curves. For the non-asymptotic case ( d and T finite), we obtain accurate approximations of the IDF curves and derive a semi-theoretical formula for the index k of the GEV model that best approximates the distribution of the annual maximum over a finite range of return-period intensities. The non-asymptotic analysis explains several observed deviations of rainfall extremes from the asymptotic predictions, such as the tendency of k to decrease as the averaging duration d increases and the tendency of the IDF curves to converge as d or the return period T increase.

Description: Remaining oil saturation established by waterflooding was measured in Indiana limestone in its original, water-wet state and under mixed-wet conditions established by adding organic acid to the oil phase. The porous plate technique was used to establish initial oil saturations ranging from S nwi = 0.23 to 0.93 under capillary-dominated conditions. For water-wet conditions, the residual oil saturation increased linearly with its initial saturation. In contrast, the remaining oil saturation under mixed-wet conditions, S nw , displayed three distinct regimes. First, S nw increased with its initial saturation up to S nwi = 0.58. Next, S nw decreased from S nwi = 0.58 to 0.76. Finally, S nw increased again as S nwi approached one. The non-monotonic dependence of S nw on S nwi at S nwi 〉 0.5 is well described by a concave-up quadratic function, and may be a salient feature of mixed-wet rocks.

Description: We present a general phenomenological formalism for the modeling of hydraulic head behaviour in naturally fractured aquifers. A non local in time version of the double porosity model is developed for Euclidean and fractal reservoirs. In the fractal case, time non-locality allows to find the geometric and topological factors responsible for subdiffusive behaviour in such heterogeneous environments. Opposite to other fractal models presented in the literature Chang and Yortsos [1990], our model include dead-ends-backbone interactions instead of matrix-fracture interactions with clear and well defined scaling exponents, thus giving a better characterization of the reservoir after such parameters are estimated. Applications to field tests are discussed. In particular, a distinctive short time head behaviour during well tests is found.

Description: The publicly available global discharge database is limited in spatial and temporal coverage. Although regional exceptions exist, the population of the database has declined over the past several years. As discharge is one of the most important parameters for modeling hydrological interactions, alternative measuring techniques must be sought. In the recent past, satellite altimetry has been investigated as an alternative for monitoring inland water level. In the present study, altimetry footprints in the vicinity of river gauging stations for the Amazon, Amur, Brahmaputra, Danube, Don, Mekong, Niger, Ob and Vistula rivers are analyzed for a functional relationship between the water level measurements from altimetry and discharge from the gauging stations. Such a functional relationship is conventionally established via a rating curve computed using simultaneous data. This study proposes a statistical approach based on quantile functions to infer this functional relation without the need for having synchronous datasets. The statistical approach provides the opportunity of extracting discharge values from altimetry data for rivers like the Mekong, Brahmaputra, Don and Vistula for which the discharge measurements at the selected gauges were made before the age of satellites. The algorithm is then validated over those rivers which do have discharge measurements available within periods of altimetry. Our validation shows that our algorithm is in the same quality range as the conventional approach. We are thus able to salvage pre-satellite altimetry discharge data and turn them into active use for the satellite altimetry time frame.

Description: Ceramics have played a crucial role in the development of fission based nuclear power, in glass & glass composite high level wasteforms, in composite cements to encapsulate intermediate level wastes (ILW) and also for oxide nuclear fuels based on UO 2 and PuO 2 /UO 2 mixed oxides. They are also used as porous filters with the ability to absorb radionuclides (RN) from air and liquids and are playing a key role in the cleanup at Fukushima. Non-oxides also find current fission applications including in graphite moderators and B 4 C control rods. Ceramics will continue to be significant in the near-term expansion of nuclear power via next-step developments of fuels with inert matrices or based on thoria and in wasteforms using alternative composite cements or single or multiphase ceramics that can host Pu & other difficult RN. Longer term advances for Generation IV reactors, which will operate at higher temperatures & with higher fuel burn-up require innovative fuel developments potentially via carbides & nitrides or composite fuel systems. Novel non-thermal (cement-like) and thermal techniques are currently being developed to treat some of the difficult legacy wastes. Non-thermally derived wasteforms developed from geopolymers, composite cements, hydroceramics, and phosphate-bonded ceramics and thermally derived wasteforms made by Hot Isostatic Pressing and fluidized bed steam reforming (FBSR) as well as vitrification techniques based on cold crucible melting (CCM), Joule-heater in-container melting and plasma melting (PM) are described. Future developments in waste treatment will be based on separation technologies for partitioning individual RN along with design & construction of RN-containing ceramic targets for inducing transmutation reactions. Near demonstration actinide-hosting ceramic wasteforms including multiphase Synroc systems are described. Opportunities also exist for ceramics in structural applications in Generation IV reactors such as composite SiC / SiC and C / C for fuel cladding and control rods and MAX phases and ultrahigh-temperature ceramics (UHTCs) may find near core fuel coating and cladding applications. Uses of ceramics in fusion reactor systems will be both functional (ceramic superconductors in magnet systems for plasma control and in Li silicate breeder blankets in tokamaks) and structural including as sapphire diagnostic windows, graphite diverters, and plasma facing C and UHTCs. In all these cases, performance is limited by poorly understood radiation damage and interface controlled processes, which demands a combined modeling/experimental approach.

Description: P and S relative arrival time residuals from teleseismic earthquakes recorded on over 60 temporary AfricaArray broadband seismic stations deployed in Uganda, Tanzania and Zambia between 2007 and 2011 have been inverted, together with relative arrival time residuals from earthquakes recorded by previous deployments, for a tomographic image of mantle wave speed variations extending to a depth of 1200 km beneath eastern Africa. The image shows a low wave speed anomaly (LWA) well developed at shallow depths (100-200 km) beneath the Eastern and Western branches of the Cenozoic East African rift system and northwestern Zambia, and a fast wave speed anomaly at depths ≤ 350 km beneath the central and northern parts of the East African Plateau and the eastern and central parts of Zambia. At depths ≥350 km the LWA is most prominent under the central and southern parts of the East African Plateau and dips to the southwest beneath northern Zambia, extending to a depth of at least 900 km. The amplitude of the LWA is consistent with a ~150-300 K thermal perturbation, and its depth extent indicates that the African superplume, originally identified as a lower mantle anomaly, is likely a whole mantle structure. A superplume extending from the core-mantle boundary to the surface implies an origin for the Cenozoic extension, volcanism and plateau uplift in eastern Africa rooted in the dynamics of the lower mantle.

Description: In the Garibaldi Belt, the northern segment of the Cascade arc, basalts at Bridge River Cones, Salal Glacier, and Mt. Meager (BSM volcanic centers) are alkalic, atypical for an arc setting. Subduction signatures are negligible or absent from primitive alkalic basalts from Salal Glacier and Bridge River, while altered oceanic crust may have contributed a minimal amount of fluid at Mt. Meager. More evolved BSM basalts display trace element signatures considered typical of arc lavas, but this is a consequence of deep crustal assimilation rather than primary input from the subducted slab. Primary BSM basalts represent 3-8% melts that segregated from enriched garnet lherzolite at significantly higher temperatures and pressures (70-105 km) than calc-alkaline Cascade arc basalts. The BSM mantle source is significantly more incompatible element-enriched than the depleted mantle tapped by calc-alkaline Cascade arc basalts. The BSM basalts are also isotopically distinct from calc-alkaline Cascade arc basalts, more similar to MORB and intraplate basalts of the NE Pacific and NW North America. The relatively deep, hot, and geochemically distinct mantle source for BSM basalts is consistent with upwelling asthenosphere. The BSM volcanic centers are close to the projected trace of the Nootka fault, which forms the boundary between the subducting Juan de Fuca plate and the near-stagnant Explorer plate. A gap or attenuated zone between the plates may promote upwelling of enriched asthenosphere that undergoes low-degree decompression melting to generate alkalic basalts that are essentially free of slab input yet occur in an arc setting.

Description: The temporal evolution of the mantle melting processes in the Asal Rift is evaluated from the chemical composition of 56 new lava flows sampled along 10 km of the rift axis and 9 km off-axis (i.e., erupted within the last 620 ky). Petrological and primary geochemical results show that most of the samples of the inner floor of the Asal Rift are affected by plagioclase accumulation. Trace element ratios and major element compositions corrected for mineral accumulation and crystallization show a symmetric pattern relative to the rift axis and preserved a clear signal of mantle melting depth variations. While FeO, Fe 8.0 , Zr/Y and (Dy/Yb) N decrease from the rift shoulders to the rift axis, SiO 2 , Na/Ti, Lu/Hf increase and Na 2 O and Na 8.0 are constant across the rift. These variations are qualitatively consistent with shallow melting beneath the rift axis and deeper melting for off-axis lava flows. Na 8.0 and Fe 8.0 contents show that beneath the rift axis, melting paths are shallow, from 81 ± 4 km to 43 ± 5 km. These melting paths are consistent with adiabatic melting in normal-temperature fertile asthenosphere, beneath an extensively thinned mantle lithosphere. On the contrary, melting on the rift shoulders (from 107 ± 7 km to 67 ± 8 km) occurred beneath thicker lithosphere, requiring a mantle solidus temperature 100 ± 40 °C hotter. In this geodynamic environment, the calculated rate of lithospheric thinning appears to be 4.0 ± 2.0 cm yr -1 , a value close to the mean spreading rate (2.9 ± 0.2 cm yr -1 ) over the last 620 ky.

Description: Global Positioning System (GPS) and Differential Interferometric Synthetic Aperture Radar (DInSAR) data, collected from July 2007 to July 2008 on Mt. Etna, are analysed to define the dynamics preceding and accompanying the onset of the eruption on 13 May 2008. Short and long-term comparisons have been made on both GPS and radar data, covering similar time windows. Thanks to the availability of three GPS surveys the year before the eruption onset, an increase in the seawards movement of the NE flank of the volcano has been detected in the few months before the dike intrusion. The GPS ground deformation pattern also shows a slight inflation centred on the western side of the volcano in the pre-eruptive long-term comparison (from July 2007 to May 2008). The GPS has been integrated with DInSAR data by the SISTEM approach, to take advantage of the different methodologies and provide high spatial sampling of the 3D ground displacement pattern. We inverted the SISTEM results in order to model the pressure source causing the observed pre-eruptive inflation. The subsequent emplacement of the eruptive dike was imaged by two GPS surveys carried out on a dense network over the uppermost part of the volcano on May 6 and 13, i.e. a few days before and a few hours after the beginning of the eruption. We inverted this comparison to define the position, geometry and kinematics of the dike. The dike intrusion was also imaged by DInSAR data with temporal baselines of 2-3 months, which confirm strong displacements localized on the summit area, rapidly decreasing towards the middle flanks of the volcano, as detected by very short-term GPS data; furthermore, the comparison between DInSAR and GPS data highlighted the presence of a depressurizing source localized beneath the upper south-western area, acting just after the dike intrusion. Finally, the long period (one year) GPS and DInSAR data were integrated by SISTEM in order to finely depict the 3D ground deformation pattern with the highest spatial resolution. The long-period data allowed the complex kinematics of the volcano to be finely imaged and highlighting the interaction between flank dynamics and magma injection.

Description: While satellite based remote-sensing has provided hydrologists with valuable new datasets, integration of such datasets in operational modeling systems is usually not straightforward due to spatial or temporal resolution issues or because remote sensing does not directly measure the hydrological quantities of interest. This is the case for satellite based radar-altimetry. River level variations can be tracked using radar altimetry at a temporal resolution between 10 and 35 days, depending on the satellite, but hydrologists are typically interested in river flows rather than levels and require predictions at daily or even sub-daily temporal resolutions. One way to exploit satellite radar altimetry is therefore to combine the data with hydrological models in a data assimilation framework. In this study, radar altimetry data from 6 ENVISAT virtual stations were assimilated to a routing model of the main reach of the Brahmaputra River driven by the outputs of a calibrated rainfall runoff model. The Extended Kalman Filter was used to update the routed water volumes for the years 2008 to 2010. Model performance was improved with the Nash-Sutcliffe model efficiency for daily discharge increasing from 0.78 to 0.84. The method uses very little in situ data and is easily implemented as an add-on to hydrological models and it therefore has the potential for large scale application to improve hydrological predictions in many river basins.

Description: Management of water temperatures in the Columbia River Basin (Washington) is critical because water projects have substantially altered the habitat of Endangered Species Act (ESA) listed species, such as salmon, throughout the basin. This is most important in tributaries to the Columbia, such as the Methow River, where the spawning and rearing life stages of these cold water fishes occurs. Climate change projections generally predict increasing air temperatures across the western United States, with less confidence regarding shifts in precipitation. As air temperatures rise, we anticipate a corresponding increase in water temperatures, which may alter the timing and availability of habitat for fish reproduction and growth. To assess the impact of future climate change in the Methow River, we couple historical climate and future climate projections with a statistical modeling framework to predict daily mean stream temperatures. A K -nearest neighbor algorithm is also employed to: (i) adjust the climate projections for biases compared to the observed record and (ii) provide a reference for performing spatiotemporal disaggregation in future hydraulic modeling of stream habitat. The statistical models indicate the primary drivers of stream temperature are maximum and minimum air temperature and streamflow and show reasonable skill in predictability. When compared to the historical reference time period of 1916-2006, we conclude that increases in stream temperature are expected to occur at each subsequent time horizon representative of the year 2020, 2040, and 2080, with an increase of 0.8 ± 1.9 °C by the year 2080.

Description: Thermal remote sensing methods for mapping evapotranspiration (ET) exploit the physical interconnection that exists between land-surface temperature (LST) and evaporative cooling, employing principles of surface energy balance (SEB). Unfortunately, while many applications in water resource management require ET information at daily and field spatial scales, current satellite-based thermal sensors are characterized by either low spatial resolution and high repeatability or by moderate/high spatial resolution and low frequency. Here we introduce a novel approach to ET mapping that fuses characteristics of both classes of sensors to provide optimal spatiotemporal coverage. In this approach, coarse resolution daily ET maps generated with a SEB model using geostationary satellite data are spatially disaggregated using daily MODIS (MODerate resolution Imaging Spectroradiometer) 1-km and bi-weekly Landsat LST imagery sharpened to 30-m. These ET fields are then fused to obtain daily ET maps at 30-m spatial resolution. The accuracy of the fused Landsat-MODIS daily ET maps was evaluated over Iowa using observations collected at 8 flux towers sited in corn and soybean fields during the Soil Moisture Experiment of 2002 (SMEX02), as well as in comparison with a Landsat-only retrieval. A significant improvement in ET accuracy (reducing errors from 0.75 to 0.58 mm/d on average) was obtained by fusing MODIS and Landsat data in comparison with the Landsat-only case, with most notable improvements when a rainfall event occurred between two successive Landsat acquisitions. The improvements are further evident at the seasonal timescale, where a 3% error is obtained using Landsat-MODIS fusion vs. a 9% Landsat-only systematic underestimation.

Description: The promotion of zircon ( ZrSiO 4 ) crystallization by ZnO from a zirconium-based frit glaze was studied and the possible mechanism was discussed. X-ray diffraction was used to analyze the relative quantities of zircon and other transitional crystals in the samples. The results show that ZnO can significantly decrease the crystallization temperature of zirconium-based glaze, depress the formation of Ca 2 ZrSi 4 O 12 , and promote the devitrification of transitional crystals t - ZrO 2 and Ca 2 ZnSi 2 O 7 , as well as lead to the formation of more zircon than the ZnO -free glaze. It was also found that zircon not only can form from the interaction between t - ZrO 2 and SiO 2 but also can devitrify directly from the glass phase of zirconium-based glaze.

Description: Barium-substituted CsAlSi 2 O 6 pollucites, Cs x Ba (1− x )/2 AlSi 2 O 6 , and barium- and iron-substituted pollucites, Cs x Ba (1− x )/2 Al x Fe 1− x Si 2 O 6 and Cs x Ba 1− x Al x Fe 1− x Si 2 O 6 were synthesized with 1 ≥  x ≥ 0.7 using a hydrothermal synthesis procedure. Rietveld analysis of X-ray diffraction data confirmed the substitution of Ba for Cs and Fe for Al , respectively. The crystallographic analysis also describes the effects of three different types of pollucite substitutions on the pollucite unit cell: Ba 2+ for Cs 1+ cation results in little effect on cell dimensions, intermediate concentrations of Ba 2+ and Fe 3+ substitution result in net minor expansion due to Fe 3+ addition, and large Ba and Fe substitutions result in overall framework contraction. Elemental analysis combined with microscopy further supports the phase purity of these new phases. These materials can be used to study the stability of CsAlSi 2 O 6 as a durable ceramic waste form, which could accommodate with time Cs and its decay product, Ba . Furthermore, success in iron substitution for aluminum into the pollucite lattice predicts that redox charge compensation for Cs cation decay is possible.

Description: Nitrogen-doped mullite fibers were first synthesized through the nitridation of Al 2 O 3 – SiO 2 gel fibers in NH 3 . The results showed that nitrogen take-up began at 800°C, reached the maximum at 900°C, and then decreased with increasing temperature. The ceramic fibers nitridated at 900°C were essentially amorphous, but contained a small amount of nano-sized Al – Si spinel crystals. Mullite was formed after nitridation at 1200°C, accompanied by crystallization of χ- SiAlON and δ- Al 2 O 3 . The incorporation of nitrogen resulted in the formation of a variety of nitrogen-containing crystalline phases. The grain size of the mullite fibers can be adjusted by changing of the nitrogen content.

Description: The solubility limit of Ca in 99.99% pure α- Al 2 O 3 (alumina) was measured using a wavelength dispersive spectrometer mounted on a scanning electron microscope. Al 2 O 3 samples were equilibrated at a concentration which ensured saturation of the Al 2 O 3 grains with Ca , and were quenched in water from 1600°C. The results were compared with those from samples which were furnace cooled from 1600°C. For the quenched samples, the Ca solubility limit was found to be 51 ± 1 ppm, which is significantly larger than the solubility limit for samples which were furnace cooled (26 ± 1 ppm).

Description: A regional survey of alkaline springs in Oman and Ligurian ophiolites shows that the alkaline water compositions significantly vary from one ophiolite to the other and within the same ophiolite. The first order correlation between the Na (and K) and Cl concentrations points to fluid compositions only partly due to evaporation. The scatter around the evaporation line implies that Na and Cl may not be conservative during the alteration of the ultramafic rocks. Mg is almost entirely depleted at pH 〉 10.5 as a result of serpentine formation within the ultramafic body and of brucite (and minor hydrotalcite) precipitation at the springs. Ca accumulates in the high pH fluids and is consumed by Ca-carbonate formation at the springs, by mixing with river waters or by the CO2 supply from the atmosphere. Thermodynamic calculations show that brucite saturation is reached at pH values around 10.5 which triggers major changes in the water composition. The waters evolve from a quartz-saturated low pH continental environment to a brucite-dominated high pH serpentinizing system at low temperature. The highest water salinities are found in springs located along the basal thrust plane of the ophiolite. The highest Al concentrations are found in some springs located on the crustal side of the mantle/crust boundary. This poses the question of the hydrologic pathways and of the role of the mineralogical composition of the altered formations.

Description: The possibility of developing large solid oxide fuel cell (SOFC) stacks based upon 25 cm 2 ceramic oxide anode-supported cells is investigated. Planar fuel cells comprising strontium titanate-based anode support impregnated with active catalysts were prepared using a combination of deposition techniques. The fuel cell tests performed in a semisealed rig have shown power densities of 185 mW cm −2 at 850°C using humidified hydrogen as fuel and air as oxidant. The structure and evolution of the catalytically active impregnated materials-10 mol% Gd -doped CeO 2 and nickel- are analysed using electron microscopy at the end of the fuel cell test, revealing that a ceria and nickel layer surrounds the titanate backbone grains while ~50–150 nm spherical-like nickel particles uniformly decorate this top layer.

Description: Structural and dielectric properties of (1− x ) BaTiO 3 – x Bi ( Mg 1/2 Ti 1/2 ) O 3 ( x  = 0.1–0.5) were investigated to understand the binary system and utilize it for high-voltage, high energy density capacitors. The solubility limit for Bi ( Mg 1/2 Ti 1/2 ) O 3 in a BaTiO 3 perovskite was between x  = 0.4 and x  = 0.5. A phase with pseudocubic symmetry was formed for x  = 0.1–0.4; a secondary phase developed at x  = 0.5. Dielectric measurements showed highly diffusive and dispersive relaxor-like characteristics from 10 to 40 mol% of Bi ( Mg 1/2 Ti 1/2 ) O 3 . These compositions also showed high relative permittivity with low-temperature coefficients of permittivity over a wide range of temperatures −100°C–600°C. Relaxation behavior was quantitatively investigated using the Vogel–Fulcher model, which revealed the activation energy of 0.17–0.22 eV. Prototyped multilayer capacitors of 18 mm × 17 mm × 4 mm dimensions with a capacitance of 12.5 nF at 1 kHz were successfully constructed and demonstrated multiple charge–discharge characteristics up to 10 kV.

Description: K 3 Gd ( PO 4 ) 2 : RE 3+ (RE = Eu, Tb) are prepared by solid-state reaction and their photoluminescence (PL) properties are investigated under UV and VUV excitation, respectively. The obtained experimental data show that no energy transfer happens among the activator ions Tb 3+ or Eu 3+ under UV excitation. Under 147-nm excitation, the strongest emission intensity of K 3 Gd ( PO 4 ) 2 : RE 3+ (RE = Eu, Tb) is obtained when the activator ions Tb 3+ or Eu 3+ concentration is 0.8 mol, the integrate emission intensity of K 3 Gd 0.2 (PO 4 ) 2 :0.8Tb 3+ is about 204% of commercial phosphor Zn 1.96 SiO 4 :0.04 Mn 2+ with chromaticity coordinates of (0.340, 0.561) and the decay time of about 5.09 ms under 147-nm excitation. We analyze the experimental data and propose a possible energy-transfer mechanism under 147-nm excitation.

Description: The 0.72 Bi ( Fe 1− x Al x ) O 3 –0.28 BaTiO 3 ( x  = 0, 0.01, 0.03, 0.05, and 0.07, abbreviated as BFA x – BT ) lead-free high-temperature ceramics were prepared by the conventional ceramic processing. Systematic investigation on the microstructures, crystalline structures, dielectric and piezoelectric properties, and high-temperature stability of piezoelectric properties was carried out. The crystalline structures of BFA x –BT ceramics evolve from rhombohedral structure with x 〈  0.01 to the coexistence of rhombohedral structure and pseudocubic phases with x  ≈ 0.01, finally to pseudocubic phases when x 〉  0.03. Remarkably high-temperature stability with near-zero temperature coefficient of piezoelectric properties ( TCk p ), together with improved piezoelectric properties has been achieved for x  = 0.01 BFA x –BT ceramics. The BFA x –BT( x  = 0.01) ceramics simultaneously show the excellent piezoelectric properties of d 33  = 151 pC/N, k p  = 0.31 and super-high-temperature stability of T d  = 420°C, TCk p  = 1 × 10 −4 . It is considered that the observed strong piezoelectricity and remarkably high-temperature stability should be ascribed to the phase coexistence of rhombohedral and pseudocubic phases. The rhombohedral phases have a positive TCk p value and the pseudocubic phases possess a negative TCk p value. Thus, the TCk p value of BFA x –BT ceramics can be tuned by composition of x .

Description: [1]  This study examines the effect of gas hydrate formation on seismic wave velocities of fine-grained sediments. Synthesis of gas hydrates in fine-grained sediments has proved to be challenging, and how hydrate formation would affect the seismic wave velocities and stiffness of clay-rich sediments has not yet been fully understood. In this study, CO 2 hydrate was synthesized in remolded and partially water-saturated clayey silt sediments that were originally cored from a hydrate occurrence region in the Ulleung Basin, East Sea, offshore Korea. After achieving excess water conditions, compressional wave and shear wave velocities were measured for different hydrate saturations and under different vertical effective stresses. The results reveal that the compressional wave velocity V P and shear wave velocity V S increase and the stress-dependency of V P and V S decreases as the hydrate saturation S H increases from 0% to ~60%. In particular, the V S ‒S H trend lies between the grain-cementing model and the load-bearing model, suggesting that gas hydrate formation in clayey silt sediments causes weak cementation from a hydrate saturation less than ~28%. The weak cementation in fine-grained sediments can be explained by the breakage of hydrate bonds that are cementing grains during sediment compression and/or the innate weakness in bonding between hydrate crystals and fine mineral grains owing to the presence of unfrozen water films on clay mineral surfaces. In addition, it is found that at low S H the cementation effect on V P is masked by the high stiffness of pore-filling phases, but it becomes pronounced at S H greater than 47%.