Microsommite: crystal chemistry, phase transitions, Ising model and Monte Carlo simulations

Microsommite, ideal formula [Na₄K₂(SO₄)] [Ca₂Cl₂][Si₆Al₆O₂₄], is a rare feldspathoid that occurs in volcanic products of Vesuvius. It belongs to the cancrinite–davyne group of minerals, presenting an ABAB… stacking sequence of layers that contain six-membered rings of tetrahedra, with Si and Al cations regularly alternating in the tetrahedral sites. The structure was refined in space group P6₃ to R=0.053 by means of single-crystal X-ray diffraction data. The cell parameters are a=22.161?Å=√3a _dav, c=5.358?Å=c _dav; Z=3. The superstructure arises due to the long-range ordering of extra-framework ions within the channels of the structure. This ordering progressively decreases with rising temperature until it is completely lost and microsommite transforms into davyne. The order–disorder transformation has been monitored in several crystals by means of X-ray superstructure reflections and the critical parameters T _c?≈?750?°C and β?≈?0.12 were obtained. The kinetics of the ordering process were followed at different temperatures and the activation energy was determined to be about 125?kJ?mol^?1. The continuous order–disorder phase transition in microsommite has been discussed on the basis of a two-dimensional Ising model in a triangular lattice with nn (nearest neighbours) and nnn (next-nearest neighbours) interactions. Such a model was simulated using a Monte Carlo technique. The theoretical model well matches the experimental data; two phase transitions were indicated by the simulated runs: at low temperature only one of the three sublattices begins to disorder, whereas the second transition involves all three sublattices.     

Structural and vibrational behaviour of fluorapatite with pressure. Part I: in situ single-crystal X-ray diffraction investigation

Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β _a =3.32(8)?10^?3 and β _c =2.40(5)?10^?3 GPa^?1, giving a ratio β _a :β _c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K ₀=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?ų at room pressure to 44.78?ų at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.     

Application of the photoacoustic method for characterization of natural galena (PbS)

Electron transport properties of single crystal and polycrystalline natural mineral galena (PbS) samples from the Trep?a mine, Yugoslavia, were determined using the photoacoustic frequency transmission technique. Their thermal diffusivity (D _T≈0.16 × 10^?5 m² s^?1), the coefficient of diffusion (D between 0.15×10^?2 0.16×10^?2 m² s^?1) and lifetime of the excess carrier (τ≈35 μs and the front and rear recombination velocity (s _g≈65.5 m s^?1 and s _b≈66.4 m s^?1, respectively), were calculated by comparing the experimental results and the theoretical photoacoustic amplitude and phase signals. The lattice parameter obtained by X-ray work was a?=5.936?Å. The free carrier concentration of these single-crystal samples was measured using the Hall method (N?=?3×10¹⁸ cm^?3). Measurements of the optical reflectivity of the same samples, as a function of wavelength, in the infrared and far infrared ranges, were performed. In the far infrared range a free electron plasma frequency was observed and numerically analyzed, using the least-squares fitting procedure. The values of optical parameters were calculated and the value of the free carrier concentration obtained by the Hall method was confirmed.     

Application of a solute transport model under variable velocity conditions in a conduit flow aquifer: Olalde karst system, Basque Country, Spain

A model based on numerical solutions, which allows for solving the dispersion equation under variable recharge and velocity conditions, is developed to simulate solute transport in conduit flow aquifers during flow recession periods. As an example, the evolution of a tracer in the little known karst conduit that links the sinking stream of Oma valley to the Olalde spring is investigated in the karstic region of Santa Eufemia-Ereñozar (Basque Country, Spain). The model, with different hypothetical structures, allows for obtaining series of tracer breakthrough curves, which are fitted to experimental data using an optimization algorithm. These results, although they can be used to simulate the tracer evolution between the two points considered, do not allow for determining the internal structure and spatial disposition of contributions in the aquifer.     

The Hg geochemistry of a geothermal stream, Steamboat Creek, Nevada: natural vs. anthropogenic influences

 A series of water samples from Steamboat Creek, Nevada, was analyzed for total mercury concentrations. Concentrations from these waters were 40 to 60 times higher than the pristine mountain streams entering the creek. The major source of the mercury entering Steamboat Creek is probably from gold/silver processing that took place in the 1860s. Received: 10 March 1997 · Accepted: 2 September 1997     

Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

The crystal chemistry and Fe<Superscript>II</Superscript>–site properties of aluminosilicate garnet solid solutions as revealed by Mössbauer spectroscopy and electronic structure calculations

The three binary garnet solid solutions Fe^II₃Al₂Si₃O₁₂–X^II₃Al₂Si₃O₁₂ (X^II= Mg^II, Mn^II, Ca^II) have been investigated by ⁵⁷Fe Mössbauer spectroscopy at 298 and 77 K and by electronic structure calculations in the local spin density approximation. The spectra yield isomer shifts and quadrupole splittings that are typical for Fe^II in the dodecahedral X-site of 222 point symmetry and are similar for each of the three binaries recorded. Conversely, electronic structure calculations based on the experimental crystal structure of the different end-member garnets exhibit pronounced variations in some of the electronic properties of Fe^II that are not reflected in the spectroscopic data. These results are interpreted as indicating that the different X–O bonds in garnet solid solutions retain to a large degree the intrinsic lengths that they possess in their respective end members, and that the Fe–O bond does not change greatly as a function of composition. This is evidence for the state of alternating bonds and not for the virtual crystal approximation in describing the X–O bond types or lengths in aluminosilicate garnet solid solutions. The observed degree and behavior of the Fe^II doublet asymmetry in the Mössbauer spectra for the three solid solution series do not indicate major variations in the anisotropic recoil-free fraction of Fe^II. Variations in doublet asymmetry are more likely a result of complex next-nearest X-site neighbor interactions and/or some degree of short-range cation ordering, though doublets representing different local X-site cation configurations cannot be resolved or fitted to the experimental spectra.     

Analysis of groundwater discharge with a lumped-parameter model, using a case study from Tajikistan

 A lumped-parameter model of groundwater balance is proposed that permits an estimate of discharge variability in comparison with the variability of recharge, by taking into account the influence of aquifer parameters. Recharge–discharge relationships are analysed with the model for cases of deterministic and stochastic recharge time-series variations. The model is applied to study the temporal variability of groundwater discharge in a river valley in the territory of Tajikistan, an independent republic in Central Asia. Received, April 1996 Revised, August 1997 Accepted, March 1998     

WEKU – a GIS-Supported stochastic model of groundwater residence times in upper aquifers for the supraregional groundwater management

 The supraregional GIS-supported stochastical model, WEKU, for the determination of groundwater residence times in the upper aquifers of large groundwater provinces is presented. Using a two-dimensional analytical model of groundwater flow, groundwater residence times are determined within two extreme cases. In the first case, maximal groundwater residence times are calculated, representing the part of groundwater, that is drained by the main surface water of a groundwater catchment area. In the second case, minimal groundwater residence times for drainage into the nearest surface water are determined. Using explicit distribution functions of the input parameters, mean values as well as potential ranges of variations of the groundwater residence times are derived. The WEKU model has been used for the determination of groundwater residence times throughout Germany. The model results – mean values and deviations of the groundwater velocity and the maximal and minimal groundwater residence times in the upper aquifers – are presented by general maps and discussed in detail. It is shown that the groundwater residence times in the upper aquifer vary regionally, differentiated between less than 1 year and more than 2000 years. Using this information, the time scales can be specified, until measures to remediate polluted groundwater resources may lead to a substantial groundwater quality improvement in the different groundwater provinces of Germany. With respect to its supraregional scale of application, the WEKU model may serve as a useful tool for the supraregional groundwater management on a state, federal or international level. Received: 15 August 1995 · Accepted: 15 October 1995     

Origins and development of Holocene coral reefs: a revisited model based on reef boreholes in the Seychelles, Indian Ocean

 Until recently, concepts of coral reef growth and accumulation have been predominantly based on a Darwinian model. In this, the upwards and outwards growth of a reef core (a coral framework) takes place over a foreslope consisting of reef talus, with the simultaneous filling of the back-reef lagoon by reef-derived debris. The principal adaptations of this pattern relate to the influence of relative changes in sea level and commonly ignore oceanographic factors such as storm frequency and severity. Boreholes through the outer edge of a fringing reef in the Seychelles, western Indian Ocean, reveal a record of Holocene sediment accumulation first established approximately 8 ka ago. Faunal and floral associations show that growth of this body began in relatively deep water but that this shallowed to <5 m within 1 ka. Subsequent accumulation was of “keep-up” style but, as the rate of sea-level rise slowed, shoaling became more frequent and aggradation was limited by reducing accommodation space. Constructional facies are characterised either by massive corals, including Leptastrea, Porites and faviids, or by branching corals, typically Acropora of the danai-robusta group. Coral surfaces may be encrusted by red algae, foraminifera and vermetids, and are commonly bored by filamentous algae, clionids and molluscs. However, detrital facies are volumetrically dominant, and the paucity of a constructional framework requires a re-evaluation of models of reef accretion. New models relate the geometry of accretion to the interplay between extreme storm events and fairweather hydrodynamic conditions. These suggest that a contiguous framework forms in areas of moderate fairweather energy without extreme storm events. Severe storms destroy the continuity of reef structures and generate increasing volumes of coarse detritus. Low storm severity, coupled with low fairweather hydrodynamic energy, may promote the accumulation of fine-grained reef-derived sediments that inhibit framework growth. While ecology reflects year-by-year sea conditions, lithology and structure are controlled by exceptional storms, with the effects of changing sea level superimposed. Received: 30 November 1998 / Accepted: 4 November 1999     

The regional park of the Nebrodi Mts. (Sicily): a contribution to an integrated groundwater management

 The Nebrodi Park, located in the north-eastern sector of Sicily, is of particular environmental and scientific interest. This is due to the morphological heterogeneity of the protected region that presents a wide variety of landscapes and ecosystems. In spite of the recent efforts of the Regional Government and Municipalities, environmental resources, especially groundwater, risk progressive depauperation and pollution. In this paper, the authors consider the hydrogeological karst unit of Monte Traura-Rocche del Crasto, the most productive in the Nebrodi belt (zone B of the regional park). This unit is underexploited and needs a careful hydrogeological study in order to supply coastal aquifers. Geochemical and geophysical prospecting has been carried out in this area. Analyses of water springs, sampled in different seasons, have suggested patterns of groundwater circulation. Apparent resistivity measurements have yielded complementary information about the recharge processes of deep aquifers. Goals of the project to which this research belongs are the rational exploitation and protection of reservoirs such as Monte Traura and the recovery of the degraded aquifers, proposing new strategies of regional management for the water resources in this comer of Sicily. Received: 27 November 1996 · Accepted: 5 January 1998