Kinetics of dehydration of Ca-montmorillonite

Isothermal thermogravimetric experiments have been carried out to determine the reaction kinetics of the dehydration processes in fuller's earth, a natural Ca-montmorillonite. Dehydration in swelling clays is a complex reaction, and analysis of the thermogravimetric data using empirical rate equations and time-transformation analysis reveals that the nature of the rate controlling mechanism is dependent upon both the temperature regime of the sample as well as the extent of reaction. For fuller's earth, we find that the dehydration kinetics are dominated by a nucleation and growth mechanism at low temperatures and fractions transformed (stage I), but above 90 °C the last stages of the reaction are diffusion controlled (stage II). The activation energy for dehydration during stage I is around 35 kJ · mol⁻¹, whereas the removal of water during stage II requires an activation energy of around 50 kJ · mol⁻¹. These two stages of dehydration are associated with primary collapse of the interlayer (stage I) and movement of water that is hydrated to cations within the interlayer (stage II). Received: 28 August 1998 / Revised, accepted: 27 January 1999     

Detrital zircon age and provenance constraints on late Paleozoic ice-sheet growth and dynamics in Western and Central Australia

U–Pb dating and Hf-isotope provenance analysis of detrital zircons from the glaciogenic lower Permian Grant Group of the Canning Basin indicate sources principally from basement terranes in central Australia, with subordinate components from terranes to the south and north. Integrating these data with field outcrop and subsurface evidence for ice sheets, including glacial valleys and striated pavements along the southern and northern margins of the basin, suggests that continental ice sheets extended over several Precambrian upland areas of western and central Australia during the late Paleozoic ice age (LPIA). The youngest zircons constrain the maximum age for contemporaneous ice sheet development to the late Carboniferous (Kasimovian), whereas palynology provides a minimum age of early Permian (Asselian–Sakmarian). Considering the palynological age of the Grant Group within the context of regional and global climate proxies, the main phase of continental ice sheet growth was possibly in the Ghzelian–Asselian. The presence of ice sheets older than Kasimovian in western and central Australia remains difficult to prove given a regional gap in deposition possibly covering the mid-Bashkirian to early Ghzelian within the main depocentres and even larger along basin margins, and the poor evidence for older Carboniferous glacial facies. There is also no evidence for extensive glacial facies younger than mid-Sakmarian in this region as opposed to eastern Australia where the youngest regional glacial phase was Guadalupian.     

High-pressure behaviour and equation of state of calcite, CaCO3

The high-pressure response of the cell parameters of calcite, CaCO₃, has been investigated by single crystal X-ray diffraction. The unit cell parameters have been refined from 0 to 1.435?GPa, and the linear and volume compressibilities have been measured as β _a =2.62(2)?×?10^?3?GPa^?1,β _c =7.94(7)?×?10^?3?GPa^?1, β _v =13.12?×?10^?3?GPa^?1. The bulk modulus has been obtained from a fit to the Birch-Murnaghan equation of state, giving K ₀=73.46?±?0.27?GPa and V ₀=367.789 ±?0.004?ų with K′=4. Combined with earlier data for magnesite, ankerite and dolomite, these data suggest that K ₀ V ₀ is a constant for the Ca-Mg rhombohedral carbonates.     

The interaction of tectonics,climate and eustasy in controlling dolomitization: A case study of Cenomanian–Turonian,shallow marine carbonates of the Iberian Basin

During the Cretaceous, high global sea-level and low latitudinal temperature variations led to the growth of epeiric carbonate platforms. Platform-scale dolomitization of these platforms is not common, reflecting the low Mg/Ca ratio of seawater and a humid climate. This study describes the processes governing pervasive dolomitization of a land-attached carbonate platform within the Iberian Basin. Dolomite is planar to sub-planar with a geochemical signature consistent with dolomitization from penesaline seawater. Dolomitization was most pervasive during a 1 Myr period in the middle Cenomanian, by repeated reflux of seawater from brine pools formed on the top of a southward-prograding carbonate platform. Tilting and structural reorganization in the Upper Cenomanian led to a reversal in polarity of the platform, and dolomitization was restarted by the northward reflux of seawater. Rising relative sea-level and oceanic acidification led to back-stepping of the platform such that the supply of dolomitizing fluids was cut off. In the Lower Turonian, pervasively dolomitized rudist rudstone facies in the south of the study area indicate that dolomitization restarted, either penecontemporaneously or later, from highly evaporated Campanian–Maastrichtian seawater. A systematic increase in dolomite crystal size up-section ties broadly, but not entirely, to stratigraphy. It is possible that these textural differences reflect changes in fluid chemistry, limestone permeability or precursor rock texture. However, the lack of stratigraphic conformance, and the preservation of the earliest-formed dolomite only in the oldest sediments, could indicate a progressive recrystallization of early-formed dolomite through repeated reflux of brines. As such, the succession appears to preserve a fossilized record of dolomite recrystallization through time during the Cenomanian–Turonian. The results of this study therefore provide a record of the progressive dolomitization of a carbonate platform and demonstrate the important interplay of climate and basin-scale tectonics on dolomite distribution and crystallinity.     

High speed photon-counting imager using a position sensitive diode

A new use for a 2-dimensional position sensitive diode (PSD) is described. A duolateral PSD was used with a microchannel plate image intensifier as a proof-of-concept photon counting (event driven) imager for astronomical imaging and photometry. This produced an imager capable of counting 25–30 kcps over the astronomical bands B, V & R, with an overall efficiency of ∼19%.     

The effect of Al/Si disorder on the I \bar 1-P \bar 1Co-Elastic phase transition in Ca-rich plagioclase

The influence of Al/Si disorder in the anorthite tetrahedral framework upon the I \(\bar 1\) -P \(\bar 1\) displacive transition of that framework has been investigted at high-temperature by powder X-ray diffraction. The temperature-dependence of the order parameter in a heat-treated (disordered) anorthite and a Ca-rich plagioclase has been determined from spontaneous strain measurements. Both samples show appreciable disorder, with Q _od = 0.88 in both cases. In each, the critical exponent β appears to be intermediate between values for classical tricritical (1/4) and second-order (1/2) phase transitions. This critical behaviour is consistent with a Landau potential in which the coefficient of the quartic term is positive but smaller than the coefficient of the sixth order term, corresponding to a second-order phase transition close to a tricritical point. There does not appear to be any defect strain tail near T _c and inhomogeneities in Q _od appear to be on rather a short length scale in these samples. The role of changing Q _od appears to be more important than that of changing composition (albite component). The data are interpreted using a model of a homogeneous field due to changing Q _od which renormalizes the transition temperature, T _c ^* , and the fourth order coefficient, B _eff, in the Landau expansion. The results are consistent with classical Landau behaviour, and demonstrate the care which must be taken in interpreting apparently non-classical critical exponents for phase transitions close to a tricritical point.     

The interior rifts of the Yemen - analysis of basin structure and stratigraphy in a regional plate tectonic context

The full extent of Mesozoic rift basins within interior Yemen has only recently been established. This work presents a detailed documentation of the stratigraph)., structure and basin development of the Marib-Shabwa and Sirr-Sayun basins, and the Jeza Trough. Yemen is located at the south-western margin of the Arabian Plate, which for most of its early geological history formed part of the northern passive margin of Gondwanaland. Mesozoic break up of the super-continent was associated with major rifting in the Late Jurassic (main phase) and Early Cretaceous. Orientation of the rift basins reflects an inheritance from deep-seated Precambrian structural trends which cross the Arabian Plate. The resultant structure of basement highs, tilted fault blocks, marginal terraces and central graben highs is illustrated in a series of detailed cross-sections. A comprehensive stratigraphic framework has also been established for the Jurassic and Cretaceous basin-fill, enabling thickness and facies variations to be analysed. This reveals a clear shift in the main period of fault-related, high sediment accumulation rates, both within and across the three interior basins of Yemen. In the western Marib-Shabwa Basin, the fill is dominantly Late Jurassic, whilst the eastern Shabwa Basin and Sirr-Sayun Basin exhibit a progressively increased, and younger, Early Cretaceous fill. The main period of fault-related sedimentation in the most easterly basin, the Jeza Trough, is wholly Cretaceous. Plate tectonic reconstructions of the area for this period have documented the separation and subsequent north-eastward movement of the Indian Plate, away- from Africa-Arabia. We believe this may have been the causal mechanism in the progressive eastward migration of rift activity in the Yemen.     

OH in zoned amphiboles of eclogite from the western Tianshan,NW-China

Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member ( ^B Na₂ ^C M²⁺ ₃ M³⁺ ₂ ^T Si₈(OH)₂) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition ( ^A _0.5 ^B Ca_1.5Na_0.5 ^C M ²⁺ _4.5 M _0.5^{3+ T} Si_7.5Al_0.5(OH)₂) (A = Na and/or K; M ²⁺ = Mg and Fe²⁺; M ³⁺ = Fe³⁺ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm⁻¹) which can be attributed to a local O(3)-H dipole surrounded by ^{M(1) M(3)}Mg₃, ^{M(1) M(3)}Mg₂Fe²⁺ and ^{M(1) M(3)} Fe²⁺ ₃, respectively, an empty A site and ^T Si₈ environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm⁻¹) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism.     

Low-temperature behaviour of ammonium ion in buddingtonite [N(D/H)<Subscript>4</Subscript>AlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>] from neutron powder diffraction

The structural response of buddingtonite [N(D/H)₄AlSi₃O₈] on cooling has been studied by neutron diffraction. Data have been collected from 280 K down to 11 K, and the crystal structure refined using the Rietveld method. Rigid-body constraints were applied to the ammonium ion to explore the structural properties of ammonium in the M-site cavities at low-temperature. Low-temperature saturation is observed for almost all the lattice parameters. From the present in situ low-temperature neutron diffraction studies, there is no strong evidence of orientational order–disorder of the ammonium ions in buddingtonite.     

Atomistic simulation of the structure and segregation to the (0001) and surfaces of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

The segregation of ten isovalent impurities (Al³⁺ Cr³⁺, Eu³⁺, Gd³⁺, Ho³⁺, La³⁺, Lu³⁺, Nd³⁺, Tb³⁺, Y³⁺) to the and the (0001) surfaces of haematite (-Fe₂O₃) have been studied using atomistic simulation where the forces between the atoms are modelled using the Born model of solids. Segregation is found to be energetically favoured in virtually every case. The results for the surface show that the most favourable impurity surface concentration is 33.33%. The (0001) surface has two possible terminations, one terminated by iron atoms and the other by oxygen. No minimum is calculated for the Fe termination of the (0001) surface at low temperatures, but when the effect of raising the temperature is considered, an energy minimum is found, also at 33.33% impurity coverage. In contrast, the O terminated (0001) surface has a minimum in the segregation energy for between 16.67 and 33.33% depending on the cation being considered.