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     

Numerical Analysis of Space–Time Finite Element Formulations for Miscible Displacements

A finite element formulation is proposed to approximate a nonlinear system of partial differential equations, composed by an elliptic subsystem for the pressure–velocity and a transport equation (convection–diffusion) for the concentration, which models the incompressible miscible displacement of one fluid by another in a rigid porous media. The pressure is approximated by the classical Galerkin method and the velocity is calculated by a post-processing technique. Then, the concentration is obtained by a Galerkin/least-squares space–time (GLS/ST) finite element method. A numerical analysis is developed for the concentration approximation. Then, stability, convergence and numerical results are presented confirming the a priori error estimates.     

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     

Towards New Swedish Recommendations for Cautious Perimeter Blasting

A Swedish table of blast damage depths has, in one form or other, been in use since the late-1970s. Its history and the underlying theory are described. New experimental and theoretical findings that point out a number of shortcomings in the table and the underlying theory are presented and discussed. A revised version of the blast damage table was recently introduced in conjunction with new but incomplete recommendations for cautious perimeter blasting. The new table leaves the difficult task of taking into account factory like decoupling, water in the borehole, the rock properties, type of initiation, charge length and the actual bit diameter to the user. This paper discusses different ways of doing this, based on the experimental findings and a recent formula for the prediction of the lengths of radial cracks behind the half-casts. The material presented in this paper is meant to supplement and extend the new Swedish recommendations for cautious perimeter blasting of tunnels, shafts, pits and road cuts.     

Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth''s mantle: an experimental study

We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na₂CO₃–H₂C₂O₄·2H₂O–C>K₂CO₃–H₂C₂O₄·2H₂O–C>>Na₂CO₃–C>K₂CO₃–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na₂CO₃ melt, and an octahedron in the K₂CO₃ melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.     

Intercomparison of IRS-P4-MSMR derived geophysical products with DMSP-SSM/I and TRMM-TMI finished products

In this paper, MSMR geophysical products like Integrated Water Vapour (IWV), Ocean Surface Wind Speed (OWS) and Cloud Liquid Water (CLW) in different grids of 50, 75 and 150 kms are compared with similar products available from other satellites like DMSP-SSM/I and TRMMTMI. MSMR derived IWV, OWS and CLW compare well with SSM/I and TMI finished products. Comparison of MSMR derived CLW with that derived from TMI and SSM/I is relatively in less agreement. This is possibly due to the use of 37 GHz in SSM/I and TMI that is highly sensitive to CLW, while 37 GHz channels are not available on MSMR. Monthly comparison of MSMR geophysical products with those from TMI is all carried out for climatological purpose. The monthly comparisons were much better compared to instantaneous comparisons. In this paper, details of the data analysis and comparison results are presented. The usefulness of the MSMR vis-à-vis other sensors is also discussed.     

Hydraulic Characteristics of Rough Fractures in Linear Flow under Normal and Shear Load

Summary A hydro-mechanical testing system, which is capable of measuring both the flow rates and the normal and shear displacement of a rock fracture, was built to investigate the hydraulic behaviour of rough tension fractures. Laboratory hydraulic tests in linear flow were conducted on rough rock fractures, artificially created using a splitter under various normal and shear loading. Prior to the tests, aperture distributions were determined by measuring the topography of upper and lower fracture surfaces using a laser profilometer. Experimental variograms of the initial aperture distributions were classified into four groups of geostatistical model, though the overall experimental variograms could be well fitted to the exponential model. The permeability of the rough rock fractures decayed exponentially with respect to the normal stress increase up to 5 MPa. Hydraulic behaviours during monotonic shear loading were significantly affected by the dilation occurring until the shear stress reached the peak strength. With the further dilation, the permeability of the rough fracture specimens increased more. However, beyond shear displacement of about 7 to 8 mm, permeability gradually reached a maximum threshold value. The combined effects of both asperity degradation and gouge production, which prohibited the subsequent enlargement of mean fracture aperture, mainly caused this phenomenon. Permeability changes during cyclic shear loading showed somewhat irregular variations, especially after the first shear loading cycle, due to the complex interaction from asperity degradations and production of gouge materials. The relation between hydraulic and mechanical apertures was analyzed to investigate the valid range of mechanical apertures to be applied to the cubic law. Received June 12, 2001; accepted February 26, 2002 Published online September 2, 2002     

KARSTIC: a sensitivity method for carbonate aquifers in karst terrain

. Groundwater in karstic aquifers can be dangerously sensitive to contamination. Many cities in the western USA rely on karstic carbonate aquifers for municipal water supplies. For example, Rapid City, South Dakota, pumps more than half of its drinking water from wells in the Madison Limestone. This work examined the sensitivity of karstic aquifers to surface contamination in mountainous terrain. Where karstic carbonate aquifers are exposed at their outcrop areas, they are particularly susceptible to the introduction of contamination through diffuse recharge or through point recharge at swallow holes along streams. Residential developments in mountainous regions of the western USA are encroaching on the recharge areas of karstic aquifers. Many of these residential developments are served by onsite wastewater disposal systems such as septic tanks and drain fields, with the attendant danger of introduction of pathogens from malfunctioning treatment systems above fractured limestone which offers little filtering. Where streams disappear into karstic aquifers at swallow holes, microbial contaminants such as Giardia or Cryptosporidium are a concern, as well as potential spills, leaks, or accidents along roads near these streams. The KARSTIC method developed and modified in this work puts greater emphasis on karst features than previous sensitivity procedures such as the US Environmental Protection Agency's DRASTIC method. The modified method gives increased attention to highly sensitive areas of karstic carbonate aquifers by weighting the synergistic effects of fracturing, karst development, and swallow holes of recharging streams. In a field application, hydrogeologic maps of a watershed in the Black Hills, USA, were digitized into a geographic information system. The resulting sensitivity map and report can be used by planners, managers, and the public as a screening tool for assessing groundwater sensitivity in regions which include karstic aquifers.