Muscovite surface structure imaged by fluid contact mode AFM

The surface structure of muscovite was imaged using an atomic force microscope (AFM) in contact mode in water. The following three types of AFM images were observed: (1) those showing clearly the arrangement of hexagonal rings of SiO₄ tetrahedra; (2) those showing a hexagonal array of bright spots separated by a distance of about 5.3 Å; and (3) those changing gradually from image (2) to image (1). Image (1) successfully provides information on the tetrahedral tilt and basal surface corrugation that are particularly characteristic of dioctahedral micas. The mean unit cell dimensions for the muscovite surface measured from Image (1) were slightly longer than those of the bulk structure, due to the rehydration of the tetrahedral sheet and/or surface relaxation. Image (2) was made by varying the scan angles, even on the same surface in which Image (1) was obtained. Image (3) has information on a single plane rather than on two or more planes involving steps, kinks and so on. Therefore, what is depicted in Images (2) and (3) is not the arrangement of interlayer K ions but the basal plane of the tetrahedral sheet. Some structural relaxation of the tetrahedral sheet surface was also observed. Gradual expansion and contraction of hexagonal rings were randomly found on the muscovite surface. The surface relaxation results from a tetrahedral rotation and/or tilting after cleaving, since significant variations of both distances and bond angles between adjacent SiO₄ tetrahedra on the surface were found.     

Computational study of tetrahedral Al–Si ordering in muscovite

 The nature of Al–Si ordering across the tetrahedral sites in muscovite, K₂Al₄(Si₆Al₂O₂₀)(OH)₄, was investigated using various computational techniques. Values of the atomic exchange interaction parameters J _l were obtained. From these parameters, a two-dimensional Al–Si ordering scheme was deduced. The transition temperature T _c for this two-dimensional ordering is 1900 K. There are several possible ordering schemes in three dimensions, based on different stacking sequences of ordered sheets of tetrahedral sites. Monte Carlo simulations of both two-dimensional and three-dimensional ordering were performed, but in the three-dimensional simulation only the two-dimensional ordering is seen, implying that three-dimensional ordering is too slow to be attained during the timescale of the simulation. The effect of the three-dimensional interactions is to raise the two-dimensional ordering temperature to 2140 K. From the three-dimensional Monte Carlo simulation, the frequency of occurrence of 4Si0Al, 3Si1Al, 2Si2Al and 1Si3Al clusters was determined, which match those inferred by ²⁹Si MAS–NMR measurements reasonably well. In fact, the match suggests that the cation ordering seen in experiments corresponds to a configuration with considerable short-range order but no long-range order, similar to a state that is at a temperature just above an ordering phase transition. Received: 28 August 2000 / Accepted: 12 March 2001     

High-temperature study and thermal expansion of phlogopite

 Unit-cell dimensions of a natural phlogopite from Pargas, Finland, have been determined in the temperature interval of 27–1050 °C by X-ray powder diffraction technique. Expansion rates vary discontinuously with temperature with a break at 412 °C. Below this temperature, the linear expansions (α) for a, b and c axis lengths are 3.74 × 10⁻⁵ K⁻¹, 1.09 × 10⁻⁵ K⁻¹, and 1.19 × 10⁻⁵ K⁻¹, respectively, and above that they are 0.86 × 10⁻⁵ K⁻¹, 0.80 × 10⁻⁵ K⁻¹, and 1.93 × 10⁻⁵ K⁻¹. The volume thermal expansion coefficients are 6.26 × 10⁻⁵ K⁻¹ and 3.71 × 10⁻⁵ K⁻¹ for low-temperature and high-temperature intervals, respectively. The observed kink in the rate of thermal expansions with temperature could be due to the different mode of structural changes. Thermogravimetric analysis of the sample indicates the oxidation of iron in the temperature range of 500–600 °C and dehydroxylation as well as decomposition of phlogopite in the temperature range of 900–1200 °C. Received: 8 September 1998 / Accepted: 28 February 2000     

The study of the kinetics and the mechanism of dehydroxylation in muscovite by ESR on Fe3+

 Dehydroxylation of muscovite in the form of small lamellae at 923 <T <1173 K was studied by Electron Spin Resonance (ESR) on Fe³⁺. The kinetics of the process has been established to be described by the model of continuous nucleation on the large surface planes of the small plates. Determined by experimental data the rate constant of the process k is shown to be that of dehydroxylation itself. The activation energy obtained by data at T<1100 K is 97.5 KJ·mol⁻¹. The nonlinear dependence of ln(k) on 1/T is explained by the theory of transitions induced by the fluctuative preparation of a potential barrier as a result of thermal oscillations of ions in the lattice. At high temperatures the potential curve of the hydroxyl's proton is transformed so that it can overcome the barrier from one potential well to the other (from one hydroxyl site to the adjacent one). Such transformations of the curve can be caused by the oscillations of large structural clusters (∼1·10⁻²² kg) with the frequency ∼4.5·10¹² s⁻¹. Received: 3 August 1995 / Accepted: 13 April 1997     

Rotation and dilation deformation mechanisms for auxetic behaviour in the α-cristobalite tetrahedral framework structure

 Analytical expressions are derived for the Poisson's ratios associated with a three-dimensional network of regular, corner-sharing tetrahedra in which: (1) the tetrahedra are assumed to be rigid and free to rotate relative to each other; (2) the tetrahedra are assumed to maintain shape and orientation but are free to change size (dilate); (3) tetrahedral rotation and dilation are assumed to act concurrently. The structure has a primitive unit cell containing four tetrahedra and is analogous to the molecular structure of α-cristobalite. Strain-dependent variations in Poisson's ratio are also predicted by the models. For deformation due to tetrahedral rotation the network is found to exhibit negative Poisson's ratios in each of the three principal directions, with the magnitude of the Poisson's ratio being dependent on the angle of rotation of the tetrahedra. The behaviour of the Poisson's ratio is isotropic in the transverse plane, but anisotropic elsewhere. In the dilation model negative Poisson's ratios equal to −1 are observed for uniaxial loading in any of the principal directions, with the value being constant irrespective of tetrahedral size. The model for concurrent tetrahedral rotation and dilation allows positive as well as negative Poisson's ratios, with the values determined by the framework geometry and relative strengths of the two mechanisms. The concurrent model also offers a design route to materials and structures having ultrahigh Young's moduli. Received: 15 February 2000 / Accepted: 1 October 2000     

Thermal equations of state of dioctahedral micas on the join muscovite–paragonite

 Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms at 298, 573, 723 and 873 K, respectively. The value of (∂K _T /∂T) was −0.0146(2) GPa K⁻¹. The thermal expansion coefficient α varied from 35.7(3) × 10⁻⁶ K⁻¹ at P ambient to 20.1(3) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −3.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa, (∂K _T /∂T) −0.0109(1) GPa K⁻¹. The thermal expansion coefficient α varied from 44.1(2) × 10⁻⁶ K⁻¹ at P ambient to 32.5(2) × 10⁻⁶ K⁻¹ at P = 4 GPa [(∂α/∂P) _T = −2.9(1) × 10⁻⁶ GPa⁻¹ K⁻¹]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion is greater and its variation with pressure is smaller in Pg than in Ms. Received: 28 January 2002 / Accepted: 5 April 2002     

A crystal-chemical investigation of Cr substitution in muscovite by XANES spectroscopy

 This work introduces a novel procedure to fit the scattering features of XANES spectra. The procedure was applied and validated on a chromium-containing muscovite for which structural and crystal-chemical characterization is available from literature. The simulation, which involved clusters formed by up to 90 atoms, proved to be effective in representing the Cr local environment, even if the system is characterized by a very low metal content, as demonstrated by the extremely good correspondence with experimental data. Received: 23 May 2002 / Accepted: 6 November 2002     

AFM observations and simulations of jarosite growth at the molecular scale: probing the basis for the incorporation of foreign ions into jarosite as a storage mineral

 The growth of K-jarosite was evaluated using scanning electron microscopy (SEM), atomic force microscopy (AFM), and molecular simulations. SEM micrographs show crystals with almost quadratic and, to a minor extent, triangular faces. These were identified to be {0 1 2} and (0 0 1) faces, respectively, using an X-ray single-crystal diffractometer. These results are in agreement with molecular simulations that show that the dipole-free {0 1 2} face is the most stable surface, followed by the (0 0 1) surface, that can lower its dipole moment perpendicular to the surface during relaxation. On the {0 1 2} face, the most stable step directions were identified. From these, an idealized equilibrium growth island can be constructed when the corner energies are minimized by the successive removal of corner ions until a stoichiometric growth island is obtained. Such an equilibrium growth island is the basis for developing a spiral growth model that explains the mechanism of spiral formation as observed using AFM. Furthermore, reactive sites that are potential candidates for the incorporation of foreign ions can be located. Received: 2 January 2001 / Accepted: 30 April 2001     

The relationship between the water table and the surface flow of a losing stream, lower Medano Creek, Great Sand Dunes National Monument, Colorado

 Proposed groundwater withdrawals in the San Luis Valley of Colorado may lower the water table in Great Sand Dunes National Monument. In response, the National Park Service initiated a study that has produced a generalized conceptual model of the hydrologic system in order to assess whether a lowering of the water table might decrease the surface flow of lower Medano Creek. Based upon information obtained during the drilling of several boreholes, there appear to be five important hydrostratigraphic units underlying lower Medano Creek within the upper 30 m of the ground surface: 1. a perched aquifer overlying an aquitard located between about 5 and 6 m below the ground surface; 2. the aquitard itself; 3. an unconfined aquifer located between the upper and lower aquitards; 4. an aquitard located between about 27 and 29 m below the ground surface; and 5. a confined underlying the lower aquitard. Because the areal extent of the aquitards cannot be determined from the borehole data, a detailed conceptual model of the hydrogeologic system underlying lower Medano Creek cannot be developed. However, a generalized conceptual model can be envisioned that consists of a complex system of interlayered aquifers and leaky aquitards, with each aquifer having a unique hydraulic head. Water levels in the perched aquifer rise rapidly to their annual maximum levels in response to the arrival of the flow terminus of Medano Creek during the spring runoff event, and the location of the flow terminus is directly dependent upon the discharge of the creek. Water levels in the deeper, non-perched aquifers do not appear to fluctuate significantly in response to the arrival of the flow terminus, demonstrating that it is unlikely that the proposed groundwater withdrawals will decrease the surface flow of lower Medano Creek. Received: 27 December 1995 · Accepted: 20 February 1996     

Thermal expansion and crystal structure of FeSi between 4 and 1173 K determined by time-of-flight neutron powder diffraction

The thermal expansion and crystal structure of FeSi has been determined by neutron powder diffraction between 4 and 1173?K. No evidence was seen of any structural or magnetic transitions at low temperatures. The average volumetric thermal expansion coefficient above room temperature was found to be 4.85(5)?×?10^?5?K^?1. The cell volume was fitted over the complete temperature range using Grüneisen approximations to the zero pressure equation of state, with the internal energy calculated via a Debye model; a Grüneisen second-order approximation gave the following parameters: θ_D=445(11)?K, V ₀=89.596(8)?ų, K ₀′=4.4(4) and γ′=2.33(3), where θ_D is the Debye temperature, V ₀ is V at T=0?K, K ₀′ is the first derivative with respect to pressure of the incompressibility and γ′ is a Grüneisen parameter. The thermodynamic Grüneisen parameter, γ_th, has been calculated from experimental data in the range 4–400?K. The crystal structure was found to be almost invariant with temperature. The thermal vibrations of the Fe atoms are almost isotropic at all temperatures; those of the Si atoms become more anisotropic as the temperature increases.     

Mapping the top of the permafrost using surface direct current resistivity survey

 Data from a direct current resistivity survey and geologic logs from boreholes were used to map the top of permafrost at a remote air force installation in Alaska. This study resulted from a remedial investigation that was conducted at Eielson Air Force Base near Fairbanks, Alaska, under the federal Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) regulations. The depth and continuity of the permafrost was important in determining the fate of petroleum contamination that was inadvertently discharged to the ground during earlier air force operations. The results indicate that the top of permafrost forms a highly irregular surface. In general, however, the top of permafrost forms a diagonal ridge at the center of the contour grid that is bordered on each side by troughs. Received: 21 November 1995 · Accepted: 5 March 1996     

Heavy metal concentrations in floodplain surface soils, Lahn River, Germany

 Even relatively pristine drainage basins in industrial countries would appear to have received anthropogenic inputs of heavy metals. Investigation of floodplain surface soils in the Lahn River drainage basin, west-central Germany, indicates that the Cu concentration is 1.5 times the pre-industrial level, Pb and Zn contents twice the pre-industrial level; Cd, Co, and Cr concentrations are nearly equal to background metal values. Based on contamination standards developed for the Lahn River, floodplain soils are moderately contaminated with Pb and Zn, slightly contaminated with Cu. Metal contents are uniform across the floodplain, with the exception of a peak immediately adjacent to the Lahn River. Floodplain surface soil metal contents are less in the Lahn River basin than in larger drainage systems of Germany. Although Lahn River metalliferous sediments are presently immobile, they would, if eroded, contribute to downstream heavy metal concentrations. Consequently, metal storage in smaller drainage basins such as the Lahn should be considered in predictions of future metal loads in major river systems, for aggregate small basins could serve as significant metal contributors. Received: 21 August 1995 · Accepted: 23 January 1996     

The inherent displacive flexibility of the hexacelsian tetrahedral framework and its relationship to polymorphism in Ba-hexacelsian

 The results of a rigid unit mode (RUM) analysis of the inherent displacive structural flexibility of the tetrahedral framework of the ideal hexacelsian structure type are presented. One of the three types of RUM found to exist is characterized by modulation wave vectors perpendicular to <110> and atomic displacement patterns involving tetrahedral rotation around the parent c axis while a second type of RUM is found to be soft at any modulation wave vector and to involve tetrahedral rotation about in-plane rotation axes. It is shown how a combination of these two types of RUM motion associated with the same q=1/2<1ˉ101>^* modulation wave vector enables the outstanding crystal chemical problems and apparently mutually contradictory results as regards polymorphism in Ba-hexacelsian to be resolved. Received: 30 December 1999 / Accepted: 16 May 2000     

The chemical composition of the surface system of Peneos river, Thessaly/Central Greece

 Peneos is the mainstream for the drainage of Thessaly's basin. It contributes significantly in recharging the aquifers, as well as to the direct irrigation water, since there is intense agricultural activity in the basin of Thessaly. The investigation of the hydrochemical conditions of the surface water system of Peneos showed that the chemical composition is related to the lithology of the aquifers of the basin, the anthropogenic influence and the biological activity. The chemical composition of this system changes in time and space. The salinity decreases during the winter period, in contrast to the summer period when it increases drastically. The lower values of TDS appear in the upstream part of the river (95–124 mg/l) whereas downstream, the values of TDS increase significantly (400–632 mg/l). The hydrochemical type Ca-Mg-HCO₃ dominates the largest part of the river while it changes to NA-Cl in the estuary. The concentrations of the dissolved species in the main Peneos river are higher than in the spring waters. Peneos is the most polluted river in Greece. The concentration of the pollutants is higher at the downstream part of the river, but is lower than the accepted upper limits. The use of the surface water of the system of Peneos river for irrigation purposes based on the SAR factor is acceptable because the absorption ratio for Na and salinity are low and medium respectively. Received: 27 October 1997 · Accepted: 21 September 1998     

四川红格层状侵入体中角闪石和金云母的矿物学特征及其成因意义

红格层状岩体是峨眉山大火成岩省内带最大的赋存钒钛磁铁矿矿床的层状岩体,从底部到顶部可分为下部岩相带、中部岩相带和上部岩相带。红格岩体下部岩相带角闪(磁铁)辉石岩和角闪(磁铁)橄辉岩中角闪石含量高达5%~15%,远远高于区内其他含超大型钒钛磁铁矿矿床的层状岩体。岩体中角闪石呈嵌晶状结构,且具有均一干涉色,暗示其为岩浆成因,而非热液蚀变的产物。此外,角闪石的矿物化学特征表现为高Al2O3含量(10.5%~12.0%)、高Al/Si(0.30~0.37)和Mg/(Fe3++Fe2++VIAl)比值(1.69~2.63)以及低Si/(Si+Ti+Al)比值(0.69~0.74),进一步表明其是直接从幔源基性岩浆中结晶形成的。金云母高MgO含量(18.7%~22.9%)的特征也说明其与幔源岩浆作用有关。角闪石和金云母的成因与红格层状侵入体的地质背景相吻合,为探讨红格岩体形成过程中的物理化学条件提供了重要的矿物学依据。根据矿物电子探针成分及其化学式计算得到岩体角闪石的结晶温度为1000~1100℃,结晶压力小于2.2kbar,结晶时的氧逸度范围在NNO-0.55到NNO+0.73之间。矿物结构关系指示岩体的磁铁矿结晶早于角闪石,因此,结合MELTs模拟计算,认为红格岩体钒钛磁铁矿矿层的形成温度为1100~1165℃,氧逸度高于NNO+0.73。红格岩体下部岩相带和中部岩相带每个旋回自下而上,角闪石的Fe3+/(Fe3+/Fe2+)比值以及全岩Fe3+/Fe2+和Mt/(Mt+Ilm)比值有规律地逐渐降低,而磁铁矿V2O3含量逐渐升高,这些特征说明Fe-Ti氧化物的分离结晶导致氧逸度逐渐降低。而上部岩相带IX旋回全岩Fe3+/Fe2+和Mt/(Mt+Ilm)比值自底部到顶部随着磁铁矿V2O3含量的降低而升高,显示出与下部岩相带和中部岩相带相反的变化趋势,表明IX旋回在分离结晶过程中氧逸度是逐渐升高的,可能是受上部岩相带富P2O5母岩浆的制约。     

Thermodynamics of Al/Al avoidance in the ordering of Al/Si tetrahedral framework structures

The main driving force behind Al/Si ordering in tetrahedral framework aluminosilicates is nearest-neighbour Al/Al avoidance. Computer simulation is used to explore the direct consequences of such Al/Al avoidance. The main result is that the order-disorder transition temperature T _c falls dramatically as the concentration x of Al in the structure is reduced, and if the only interactions are those associated with nearest-neighbour Al/Al avoidance, T _c becomes zero for x less than some critical value x _c , where x _c =0.31 for the feldspar framework and x _c =0.34 for cordierite. Also a large degree of short range order is found above T _c . Both results differ radically from the standard Bragg-Williams model. Plots of entropy and enthalpy of ordering are given as functions of x and T, which may be used to interpret experimental data or for extrapolation into ranges of x and T inaccessible to experiment. Received: 14 May 1997 / Revised, accepted: 2 June 1997     

Electronic and magnetic structure of vivianite: cluster molecular orbital calculations

The electronic and magnetic structure of the octahydrophosphate vivianite, Fe₃(PO₄)₂·8H₂O, has been investigated by cluster molecular orbital calculations in local spin density approximation. Optical and Mössbauer spectra are well reproduced by the calculations, and the differences between the two iron sites can be correlated with differences in the geometrical structure of the first coordination sphere. The spin structure within the crystallographic ac plane is derived and explained on the basis of different superexchange pathways via edges of the phosphate tetrahedra. The calculations demonstrate that quite large clusters (up to 118 atoms) are necessary to arrive at reliable results.     

Hydrochemical evolution and environmental features of Salso River catchment, central Sicily (Italy)

 A hydrogeochemical study of the Salso River highlighted the chemical and isotopic space-time evolution along its flow path and the main contamination processes. Within the basin, three different hydrogeochemical facies have been individuated: (1) Ca-Mg-HCO₃, (2) Ca-Mg-SO₄ and (3) Na-Cl. The first facies reflects the chemical composition of the groundwaters hosted in the carbonate reliefs that belong to the Madonie Mountains. The second and the third facies are the result of the interaction processes between surface waters and the gypsum and salty clays, respectively. Two pollution sources have been also located in the basin downstream from the salt mine and downstream from a discharge area of wastewater from the town of Gangi. On the basis of the location of natural and anthropogenic pollution sources, the waters available for drinking and irrigation use are also indicated. Received: 16 July 1999 · Accepted: 22 December 1999     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Structural relation of hydrous ringwoodite to hydrous wadsleyite

The sequential displacement mechanism based on the oxygen-lattice cubic closest packing (c.c.p.) in the < 2 0 1 > direction was proposed in this study. All displacements of cations are within the OT and the O layers with the length of displacement vector being around 1.7 or 2.9 Å, contrary to displacement of around 5.0 Å for models proposed previously. The difference in atomic arrangement between hydrous wadsleyite and hydrous ringwoodite is small. The atomic arrangement of the O layer of hydrous wadsleyite is essentially the same as that of hydrous ringwoodite when Mg vacancies preferentially exist in the O layer. The partial occupancies of normally vacant tetrahedral sites reported in the hydrous-β and hydrous-γ structures may possibly be caused by the existence of Mg vacancies at the octahedral sites through phase transition from hydrous-β to hydrous-γ or from hydrous-γ to hydrous-β phases.