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     

A three-dimensional parametric study of the use of soil nails for stabilising tunnel faces

Applying an effective nailing system at a tunnel heading, not only improves the stability of the tunnel heading and limits deformation at the tunnel face, but it also reduces volume loss during excavation and hence reduces ground surface settlement. The effectiveness of a soil nail system is affected by many factors such as the diameter and stiffness of the nails. In this paper, a systematic parametric study was conducted to study the axial rigidity of a nail, E_nA_n, for improving the stability of tunnel headings and reducing ground movements in stiff clay. The parametric study involved a series of three-dimensional elasto-plastic coupled-consolidation finite element analyses. The stability of the tunnel face is improved with increasing E_nA_n. For a given nail density applied at the tunnel face, an optimum axial rigidity of the nail (E_nA_n)_opt can be identified. The efficiency of the nailing system diminishes when (E_nA_n)_opt is reached. The use of a soil nailing system reduces the magnitude of stress relief at the tunnel heading during excavation. Thus, this reduction of stress relief minimises the amount of soil yielding and excess pore water pressure generated in the soil around the tunnel heading.     

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     

Poroelastic analysis of cover-collapse sinkhole formation by piezometric surface drawdown

Where the water table is above the soil-rock contact in karst regions, cover-collapse sinkholes in the soil and soft sediment above the rock commonly occur as a result of drawdown of the piezometric surface in the karst aquifer. Transient stresses and pore pressures around soil voids at the soil-rock contact can cause hydraulic fracturing of the soil near the wall of the void. After the first such fracture, successive sloughing of soil propagates the soil void rapidly to the surface, resulting in a cover-collapse sinkhole. Sinkhole formation by this mechanism should be strongly a function of rate and magnitude of piezometric surface drawdown, permeability and tensile strength of the soil, and the size, depth, and geometry of the initial soil void. Large soil voids and those with walls that are partly planar or of low curvature are most susceptible to hydraulic fracture and the resulting progression to sinkhole formation.     

A Model for the polar motion of the deformable Earth adequate for astrometric data

Refined analytical expressions for the frequencies corresponding to the Chandler motion of the pole and the diurnal rotation of the deformable Earth are derived. Numerical estimates of the period and amplitude of the polar oscillations are presented. The trajectory of the Chandler polar motion derived via numerical modeling is in qualitative and quantitative agreement with experimental data from the International Earth Rotation Service (IERS). An evolutionary model describing slow variations in the Earth’s rotation parameters under the action of the dissipative moments of the tidal gravitational forces on time scales considerably longer than the precession period of the Earth’s axis is constructed. The axis of the Earth’s figure tends to approach the angular momentum vector of the proper rotation.     

Trace element mobility during sub-seafloor alteration of basaltic glass from Ocean Drilling Program site 953 (off Gran Canaria)

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.     

Origin of iodine in volcanic fluids: I results from the Central American Volcanic Arc

The largest reservoir of crustal iodine is found in marine sediments, where it is closely associated with organic material. This presence, together with the existence of a long-lived, cosmogenic radioisotope ¹²⁹I (t_1/2 = 15.7 Ma), make this isotopic system well suited for the study of sediment recycling in subduction zones. Reported here are the results of ¹²⁹I/I ratios in volcanic fluids, collected during a comprehensive study of fluids and gases in the Central American Volcanic Arc. ¹²⁹I/I ratios, together with I, Br, and Cl concentrations, were determined in 79 samples from four geothermal centers and a number of crater lakes, fumaroles, hot springs, and surface waters in Costa Rica, Nicaragua, and El Salvador. Geothermal and volcanic fluids were found to have iodine concentrations substantially higher than values in seawater or meteoric waters. ¹²⁹I/I ratios in most of the geothermal fluids are below the preanthropogenic input ratio of 1500 × 10⁻¹⁵, demonstrating that recent anthropogenic additions are largely absent from the volcanic systems. The majority of the ¹²⁹I/I ratios are between 500 and 800 × 10⁻¹⁵. These ratios indicate minimum iodine ages between 25 and 15 Ma, in good agreement with the age of subducted sediments in this region. In all four geothermal systems, however, a few samples were found with iodine ages older than 40 Ma—that is, considerably below the expected age range for subducted sediments from the Cocos Plate. These samples probably reflect the presence of iodine derived from sediments in older accreted oceanic terraines. The iodine ages indicate that the magmatic end member for the volcanic fluids originates in the deeper parts of the subducted sediment column, with small additions from older iodine mobilized from the overlying crust. The high concentrations of iodine in geothermal fluids, combined with the observed iodine ages, demonstrate that remobilization in the main volcanic zone (and probably also in the forearc area) is an important part in the overall marine cycle of iodine and similar elements.