Incorporation of Cr<Superscript>3+</Superscript> in dickite: a spectroscopic study

 We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm⁻¹ allows us to unambiguously identify the major contribution of octahedrally coordinated Cr³⁺ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr³⁺ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr³⁺ for Al³⁺ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr³⁺ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe³⁺ ions (λ≈ 0.6–0.8). Received: 29 June 2001 / Accepted: 22 October 2001     

Low-temperature thermodynamic properties of disordered zeolites of the natrolite group

 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na_1.90K_0.22Ca_0.06)[Al_2.24Si_2.76O₁₀]·nH₂O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K⁻¹ mol⁻¹ for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K⁻¹ mol⁻¹ for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C _p (298.15)=359.1 J K⁻¹ mol⁻¹, S(298.15) −S(0)=362.8 J K⁻¹ mol⁻¹. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001     

Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

A method to predict the group fissuring and faulting caused by regional groundwater decline

Ground fissuring is a recurrent problem in many countries where water extraction surpasses the natural recharge of aquifers. Due to differential settlement, the soil layer undergoes deformation and cracks with serious consequences for civil infrastructure. Here, we propose an approximate analysis of the fissuring process that can be used to predict the location of cracks, which increasingly affect some middle- and large-sized cities in the world. For that purpose, the ground loss theory is applied to sediments overlying a sinusoidal-shaped graben. This analysis shows the existence of a tensile zone at the border of the graben with maximal values on its shoulder where tension cracks are more likely to appear. It also shows that soil deformation under differential settlement may evolve into ground faulting if water withdrawal continues. Finally, when a crack has completely developed, the tensile zone shifts towards the center of the graben, creating a new area for potential cracking and faulting.     

Variation in element release rate from different mineral size fractions from the B horizon of a granitic podzol

Far-from-equilibrium batch dissolution experiments were carried out on the 2000–500, 500–250, 250–53 and 53–2 μm size fractions of the mineral component of the B horizon of a granitic iron humus podzol after removal of organic matter and secondary precipitates. The different size fractions were mineralogically and chemically similar, the main minerals present being quartz, alkali and plagioclase feldspar, biotite and chlorite. Specific surface area increased with decreasing grain size. The measured element release rates decreased in the order 53–2>>>2000–500>500–250>250–53 μm. Surface area normalised element release rates from the 2000–500, 500–250 and 250–53 μm size fractions (0.6–77×10⁻¹⁴ mol/m²/s) were intermediate between literature reported surface area normalised dissolution rates for monomineralic powders of feldspar (0.1–0.01×10⁻¹⁴ mol/m²/s) and sheet silicates (100×10⁻¹⁴ mol/m²/s) dissolving under similar conditions. Element release rates from the 53–2 μm fraction (400–3000×10⁻¹⁴ mol/m²/s) were a factor of 4–30 larger than literature reported values for sheet silicates. The large element release rate of the 53–2 μm fraction means that, despite the small mass fraction of 53–2 μm sized particles present in the soil, dissolution of this fraction is the most important for element release into the soil. A theoretical model predicted similar (within a factor of <2) bulk element release rates for all the mineral powders if observed thicknesses of sheet silicate grains were used as input parameters. Decreasing element release rates with decreasing grain size were only predicted if the thickness of sheet silicates in the powders was held constant. A significantly larger release rate for the 53–2 μm fraction relative to the other size fractions was only predicted if either surface roughness was set several orders of magnitude higher for sheet silicates and several orders of magnitude lower for quartz and feldspars in the 53–2 μm fraction compared to the other size fractions or if the sheet silicate thickness input in the 53–2 μm fraction was set unrealistically low. It is therefore hypothesised that the reason for the unpredicted large release rate from the 52–3 μm size fraction is due to one or more of the following reasons: (1) the greater reactivity of the smaller particles due to surface free energy effects, (2) the lack of proportionality between the BET surface area used to normalise the release rates and the actual reactive surface area of the grains and, (3) the presence of traces quantities of reactive minerals which were undetected in the 53–2 μm fraction but were entirely absent in the coarser fractions.     

The effect of acoustic waves on spectral-line profiles in the solar atmosphere: Observations and theory

The fine structure of the FeI λ 532.4185-nm line of neutral iron is studied with high spatial (0.5″) and temporal (9.3 s) resolution using observations of a quiet region at the center of the solar disk. The character of the line asymmetry depends strongly on the nature of the velocity field, i.e., on whether it is due to convective or wave motions. The magnitude of the asymmetry due to acoustic waves is comparable to that due to convective motions. The propagation of acoustic waves in moving granules and intergranular lanes is studied by solving a system of hydrodynamical equations in a three-dimensional model for the solar atmosphere. The temporal variations in the bisector of the line synthesized in a non-LTE approximation agree well with the observational data.     

The possible formation of massive tori in white-dwarf binary systems

Mass exchange in white-dwarf binary systems with mass ratios 0.35–0.55 and total masses exceeding the Chandrasekhar limit could lead to the disruption of the less massive component of the system and the formation of a torus around the more massive component.     

ENSO impacts on salinity in Tampa Bay, Florida

Estuarine salinity distributions reflect a dynamic balance between the processes that control estuarine circulation. At seasonal and longer time scales, freshwater inputs into estuaries represent the primary control on salinity distribution and estuarine circulation. El Niño-Southern Oscillation (ENSO) conditions influence seasonal rainfall and stream discharge patterns in the Tampa Bay, Florida region. The resulting variability in freshwater input to Tampa Bay influences its seasonal salinity distribution. During El Niño events, ENSO sea surface temperature anomalies (SSTAs) are significantly and inversely correlated with salinity in the bay during winter and spring. These patterns reflect the elevated rainfall over the drainage basin and the resulting elevated stream discharge and runoff, which depress salinity levels. Spatially, the correlations are strongest at the head of the bay, especially in bay sections with long residence times. During La Niña conditions, significant inverse correlations between ENSO SSTAs and salinity occur during spring. Dry conditions and depressed stream discharge characterize La Niña winters and springs, and the higher salinity levels during La Niña springs reflect the lower freshwater input levels.     

Carbon budget for a subtropical seagrass dominated coastal lagoon: How important are seagrasses to total ecosystem net primary production?

It has been assumed that because seagrasses dominate macrophyte biomass in many estuaries they also dominate primary production. We tested this assumption by developing three carbon budgets to examine the contribution of autotrophic components to the total ecosystem net primary production (TENPP) of Lower Laguna Madre, Texas. The first budget coupled average photosynthetic parameters with average daily irradiance to calculate daily production. The second budget used average photosynthetic parameters and hourly in situ irradiance to estimate productivity. The third budget integrated temperature-adjusted photosynthetic parameters (using Q₁₀=2) and hourly in situ irradiance to estimate productivity. For each budget TENPP was calculated by integrating production from each autotroph based on the producers’ areal distribution within the entire Lower Laguna Madre. All budgets indicated that macroalgae account for 33–42% of TENPP and seagrasses consistently accounted for about 33–38%. The contribution by phytoplankton was consistently about 15–20%, and the contribution from the benthic microalgae varied between 8% and 36% of TENPP, although this may have been underestimated due to our exclusion of the within bed microphytobenthos component. The water column over the seagrass beds was net heterotrophic and consequently was a carbon sink consuming between 5% and 22% of TENPP, TENPP ranged between 5.41×10¹⁰ and 2.53×10¹¹ g C yr⁻¹, depending on which budget was used. The simplest, most idealized budget predicted the highest TENPP, while the more realistic budgets predicted lower values. Annual production rates estimated using the third budget forHalodule urightii andThalassia testudinum compare well with field data. Macroalgae and microalgae contribute 50–60% of TENPP, and seagrass may be more important as three-dimensional habitat (i.e., structure) than as a source of organic carbon to the water column in Lower Laguna Madre.     

Empirical models relating viscosity and tracer diffusion in magmatic silicate melts

The Adam-Gibbs equations describing relaxation in silicate melts are applied to diffusion of trace components of multicomponent liquids. The Adam-Gibbs theory is used as a starting point to derive an explicit relation between viscosity and diffusion including non-Arrhenian temperature dependence. The general form of the equation is D_iη = A_iexp{Δ(s_cE_i)/TS_c}, where D is diffusivity, η is melt viscosity, T is absolute temperature, Δ(s_cE_i) is the difference between the products of activation energies and local configurational entropies for viscous and diffusive relaxation, A_i is a constant that depends on the characteristics of the diffusing solute particles, and S_c is configurational entropy of the melt. The general equation will be impractical for most predictive purposes due to the paucity of configurational entropy data for silicate melts. Under most magmatic conditions the proposed non-Arrhenian behaviour can be neglected, allowing the general equation to be simplified to a generalized form of the Eyring equation to describe diffusion of solutes that interact weakly with the melt structure: D_iη/T = Q_iexp{ΔE_i/RT}, where Q_i and ΔE_i depend on the characteristics of the solute and the melt structure. If the diffusing solute interacts strongly with the melt structure or is a network-forming cation itself, then ΔE_i = 0, and the relation between viscosity and diffusion has the functional form of the classic Eyring and Stokes-Einstein equations; D_iη/T = Q_i. If the diffusing solute can make diffusive jumps without requiring cooperative rearrangement of the melt structure, the diffusivity is entirely decoupled from melt viscosity and should be Arrhenian, i.e., D_i = Q_iexp{B_i/T}. A dataset of 594 published diffusivities in melts ranging from the system CAS through diopside, basalt, andesite, anhydrous rhyolite, hydrous rhyolite, and peralkaline rhyolite to albite, orthoclase, and jadeite is compared with the model equations. Alkali diffusion is completely decoupled from melt viscosity but is related to melt structure. Network-modifying cations with field strength Z_i²/r between 1 and 10 interact weakly with the melt network and can be modelled with the extended form of the Eyring equation. Diffusivities of cations with high field strength have activation energies essentially equal to that of viscous flow and can be modelled with a simple reciprocal Eyring-type dependence on viscosity. The values of Q_i, ΔE_i and B_i for each cation are different and can be related to the cation charge and radius as well as the composition of the melt through the parameters Z_i²/r, M/O, and Al/(Na + K + H). I present empirical fit parameters to the model equations that permit prediction of cation diffusivities given only charge and radius of the cation and temperature, composition and viscosity of the melt, for the entire range of temperatures accessible to magmas near to or above their liquidus, for magmas ranging in composition from basalt through andesite to hydrous or anhydrous rhyolite. Pressure effects are implicitly accounted for by corrections to melt viscosity. Ninety percent of diffusivities predicted by the models are within 0.6 log units of the measured values.