Comparison of heat and bromide as ground water tracers near streams

Heat and bromide were compared as tracers for examining stream/ground water exchanges along the middle reaches of the Santa Clara River, California, during a 10-hour surface water sodium bromide injection test. Three cross sections that comprise six shallow (<1 m) piezometers were installed at the upper, middle, and lower sections of a 17 km long study reach, to monitor temperatures and bromide concentrations in the shallow ground water beneath the stream. A heat and ground water transport simulation model and a closely related solute and ground water transport simulation model were matched up for comparison of simulated and observed temperatures and bromide concentrations in the streambed. Vertical, one-dimensional simulations of sediment temperature were fitted to observed temperature results, to yield apparent streambed hydraulic conductivities in each cross section. The temperature-based hydraulic conductivities were assigned to a solute and ground water transport model to predict sediment bromide concentrations, during the sodium bromide injection test. Vertical, one-dimensional simulations of bromide concentrations in the sediments yielded a good match to the observed bromide concentrations, without adjustment of any model parameters except solute dispersivities. This indicates that, for the spatial and temporal scales examined on the Santa Clara River, the use of heat and bromide as tracers provide comparable information with respect to apparent hydraulic conductivities and fluxes for sediments near streams. In other settings, caution should be used due to differences in the nature of conservative (bromide) versus nonconservative (heat) tracers, particularly when preferential flowpaths are present.     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Simulation of monsoon depressions using MM5: sensitivity to cumulus parameterization schemes

Summary The sensitivity of the simulation of the monsoon depressions to the cumulus parameterization schemes used in a numerical model is studied using the Pennsylvania State University – National Center for Atmospheric Research (PSU-NCAR) model MM5 version 3.6.2. Three different cases of monsoon depressions were studied with a two way interacting domains of 45 km and 15 km resolutions. Two different cumulus parameterization schemes namely Grell (GR) and Kain-Fritsch (KF) were used for the sensitivity study. The model was integrated for 48 hours with the initial and boundary conditions of European Center for Medium Range Weather Forecasting Reanalysis (ERA-40) data. The results show that both the schemes are able to simulate the large scale features of the monsoon depressions realistically. However, both the schemes failed to simulate the exact location of the depression after 24- and 48-hour simulation. The rainfall simulations of both the schemes were very different. The model with the GR scheme tends to over predict the rainfall. The KF scheme could simulate the distribution of the rainfall comparable to the observations. The KF scheme could simulate the maximum observed rainfall but due to locational errors of the simulated depression, the location of the maximum rainfall was not exact. It is also seen that the resolution of the model has a positive impact on the rainfall simulation. The GR and KF schemes were able to realistically simulate the apparent heat sources, but the apparent moisture profile simulated with KF scheme was more comparable to the verifying analysis. The root mean square errors of mean sea-level pressure, temperature, zonal wind and meridional wind were smaller for KF simulation compared to the GR simulation. Permanent affiliation: Center for Development of Advanced Computing, Pune University Campus, Ganeshkhind, Pune-411 007, India.     

The lunar rock and mineral characterization consortium: Deconstruction and integrated mineralogical,petrologic, and spectroscopic analyses of mare basalts

The lunar rock and mineral characterization consortium (LRMCC) has conducted coordinated mineralogy/petrography/spectroscopy analyses of a suite of pristine lunar basalts. Four basalt slabs (two low‐Ti, two high‐Ti) and paired thin sections were analyzed. Thin sections were analyzed for mineralogy/petrography, while the slabs were used to prepare particulate separates of major mineral phases and bulk samples. Mineral separates and particulate bulk samples were crushed to controlled grain sizes and their reflectance spectra measured in the NASA RELAB at Brown University. The resulting data set provides an essential foundation for spectral mixing models, offers valuable endmember constraints for space weathering analyses, and represents critical new ground truth results for lunar science and exploration efforts.     

Near‐infrared spectra of clinopyroxenes: Effects of calcium content and crystal structure

Abstract– Pyroxenes are among the most common minerals in the solar system and are ideally suited for remote geochemical analysis because of the sensitivity of their distinctive spectra to mineral composition. Fe²⁺ is responsible for the dominant pyroxene absorptions in the visible and near‐infrared, but substitutions of other cations such as Ca²⁺ change the crystal structure and site geometries and thus the crystal field splitting energies of the Fe cations. To define spectral systematics resulting from major pyroxene cations (Ca²⁺, Mg²⁺, and Fe²⁺), we focus on a suite of pyroxenes synthesized with only Ca²⁺, Mg²⁺, and Fe²⁺ in the two octahedral sites, specifically examining the effect of Ca²⁺ on pyroxene absorption bands. The modified Gaussian model is used to deconvolve pyroxene spectra into component bands that can then be linked directly to crystal field absorptions. In orthopyroxenes and low‐Ca clinopyroxenes, Ca²⁺‐content has a strong and predictable effect on the positions of the absorption bands. At a threshold of Wo₃₀, the crystal field environment stagnates and the M2 bands cease to change significantly as more Ca²⁺ is added. At Wo₅₀, when most of the M2 sites are filled by Ca²⁺, band positions do not change drastically, although the presence and strengths of the 1 and 2 μm bands are affected by even trace amounts of Fe²⁺ in the M2 site. It is thus apparent that next‐nearest neighbors and the distortions they impose on the pyroxene lattice affect the electronic states around the Fe²⁺ cations and control absorption band properties.     

Effects of atmospheric dynamics and ocean resolution on bi-stability of the thermohaline circulation examined using the Grid ENabled Integrated Earth system modelling (GENIE) framework

We have used the Grid ENabled Integrated Earth system modelling (GENIE) framework to undertake a systematic search for bi-stability of the ocean thermohaline circulation (THC) for different surface grids and resolutions of 3-D ocean (GOLDSTEIN) under a 3-D dynamical atmosphere model (IGCM). A total of 407,000 years were simulated over a three month period using Grid computing. We find bi-stability of the THC despite significant, quasi-periodic variability in its strength driven by variability in the dynamical atmosphere. The position and width of the hysteresis loop depends on the choice of surface grid (longitude-latitude or equal area), but is less sensitive to changes in ocean resolution. For the same ocean resolution, the region of bi-stability is broader with the IGCM than with a simple energy-moisture balance atmosphere model (EMBM). Feedbacks involving both ocean and atmospheric dynamics are found to promote THC bi-stability. THC switch-off leads to increased import of freshwater at the southern boundary of the Atlantic associated with meridional overturning circulation. This is counteracted by decreased freshwater import associated with gyre and diffusive transports. However, these are localised such that the density gradient between North and South is reduced tending to maintain the THC off state. THC switch-off can also generate net atmospheric freshwater input to the Atlantic that tends to maintain the off state. The ocean feedbacks are present in all resolutions, across most of the bi-stable region, whereas the atmosphere feedback is strongest in the longitude–latitude grid and around the transition where the THC off state is disappearing. Here the net oceanic freshwater import due to the overturning mode weakens, promoting THC switch-on, but the atmosphere counteracts this by increasing net freshwater input. This increases the extent of THC bi-stability in this version of the model. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Resource allocation for regional earthquake risk mitigation: a case study of Tehran,Iran

This paper presents a new optimization model to help cities in seismically active developing countries decide (1) How much to spend on pre-earthquake mitigation versus waiting until after an event and paying for reconstruction or simply not rebuilding damaged buildings? (2) Which buildings to mitigate and how? and (3) Which buildings to reconstruct and how? It extends previously developed optimization models to consider the particular issues that arise in such countries. First, the model allows for the possibility that some damaged buildings will not be reconstructed immediately and keeps track of any lost building inventory. Second, buildings can be mitigated to, or when damaged, reconstructed to, any appropriate structural type and seismic design level. Finally, the model objectives include minimizing the chance of an extremely high death toll in any one earthquake and minimizing the average annual death toll across earthquakes. The model is illustrated through a case study analysis for Tehran, Iran.     

Pauling bond strength, bond length and electron density distribution

The power law regression equation, <R(M–O)> = 1.46(<ρ(r _c)>/r)^?0.19, relating the average experimental bond lengths, <R(M–O)>, to the average accumulation of the electron density at the bond critical point, <ρ(r _c)>, between bonded pairs of metal and oxygen atoms (r is the row number of the M atom), determined at ambient conditions for oxide crystals, is similar to the regression equation R(M–O) = 1.41(ρ(r _c)/r)^?0.21 determined for three perovskite crystals at pressures as high as 80 GPa. The pair are also comparable with the equation <R(M–O)> = 1.43(<s>/r)^?0.21 determined for oxide crystals at ambient conditions and <R(M–O)> = 1.39(<s>/r)^?0.22 determined for geometry-optimized hydroxyacid molecules that relate the geometry-optimized bond lengths to the average Pauling bond strength, <s>, for the M–O bonded interactions. On the basis of the correspondence between the equations relating <ρ(r _c)> and <s> with bond length, it seems plausible that the Pauling bond strength might serve a rough estimate of the accumulation of the electron density between M–O bonded pairs of atoms. Similar expressions, relating bond length and bond strength hold for fluoride, nitride and sulfide molecules and crystals. The similarity of the expressions for the crystals and molecules is compelling evidence that molecular and crystalline M–O bonded interactions are intrinsically related. The value of <ρ(r _c)> = r[(1.41)/<R(M–O)>]^4.76 determined for the average bond length for a given coordination polyhedron closely matches the Pauling’s electrostatic bond strength reaching each the coordinating anions of the coordinated polyhedron. Despite the relative simplicity of the expression, it appears to be more general in its application in that it holds for the bulk of the M–O bonded pairs of atoms of the periodic table.