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.     

Water quality variation and clam growth: Is pH really a non-issue in estuaries?

A tandem deployment system was used to critically evaluate relationships between important water chemistry parameters (pH, salinity, dissolved oxygen) and biotic performance based on clam growth. The effects of environmental conditions on growth of juvenile clams,Mercenaria mercenaria, were determined after 7-day field deployments in cages at reference sites from 1998 to 2000. Continuous measurements of the overlying water chemistry parameters were monitored by deploying an in situ water quality instrument (Hydrolab Datasonde) at the same time. While salinity was identified as an important determinant of clam growth over wide salinity ranges (10–35‰), pH was also found to be a very important parameter, especially in low-salinity regimes (<25‰). Average pH measurements ranged from 7.2 to 7.8; minimal pHs ranged from 6.9 to 7.6. The results indicated that when average pH levels fell below 7.5 or minimum pH levels fell below 7.2, growth rates were <50% that of clams deployed under higher pH conditions. Estuarine systems are generally perceived as being well-buffered so pH is frequently assumed to be unimportant, but our results suggest that pH levels can decline in estuarine systems to levels that can adversely affect biological responses. The potential impacts on biological resources of even moderate decreases in pH, particularly in systems that naturally tend to have lower pH conditions, may be more important than previously realized.