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1.
Orthorhombic post-perovskite CaPtO3 is isostructural with post-perovskite MgSiO3, a deep-Earth phase stable only above 100 GPa. Energy-dispersive X-ray diffraction data (to 9.4 GPa and 1,024 K) for CaPtO3 have been combined with published isothermal and isobaric measurements to determine its P–V–T equation of state (EoS). A third-order Birch–Murnaghan EoS was used, with the volumetric thermal expansion coefficient (at atmospheric pressure) represented by α(T) = α0 + α1(T). The fitted parameters had values: isothermal incompressibility, $ K_{{T_{0} }} $  = 168.4(3) GPa; $ K_{{T_{0} }}^{\prime } $  = 4.48(3) (both at 298 K); $ \partial K_{{T_{0} }} /\partial T $  = ?0.032(3) GPa K?1; α0 = 2.32(2) × 10?5 K?1; α1 = 5.7(4) × 10?9 K?2. The volumetric isothermal Anderson–Grüneisen parameter, δ T , is 7.6(7) at 298 K. $ \partial K_{{T_{0} }} /\partial T $ for CaPtO3 is similar to that recently reported for CaIrO3, differing significantly from values found at high pressure for MgSiO3 post-perovskite (?0.0085(11) to ?0.024 GPa K?1). We also report axial P–V–T EoS of similar form, the first for any post-perovskite. Fitted to the cubes of the axes, these gave $ \partial K_{{aT_{0} }} /\partial T $  = ?0.038(4) GPa K?1; $ \partial K_{{bT_{0} }} /\partial T $  = ?0.021(2) GPa K?1; $ \partial K_{{cT_{0} }} /\partial T $  = ?0.026(5) GPa K?1, with δ T  = 8.9(9), 7.4(7) and 4.6(9) for a, b and c, respectively. Although $ K_{{T_{0} }} $ is lowest for the b-axis, its incompressibility is the least temperature dependent.  相似文献   

2.
The temperature dependences of the crystal structure and superstructure intensities in sodium nitrate, mineral name nitratine, NaNO3, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction. Nitratine transforms from $R{\overline{3}} c\;\hbox{to}\;R{\overline{3}} m$ at T c = 552(1) K. A NO3 group occupies, statistically, two positions with equal frequency in the disordered $R{\overline{3}} m$ phase, but with unequal frequency in the partially ordered $R{\overline{3}} c$ phase. One position for the NO3 group is rotated by 60° or 180° with respect to the other. The occupancy of the two orientations in the $R{\overline{3}} c$ phase is obtained from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x ? 1, where S is 0 at T c and 1 at 0 K. The NO3 groups rotate in a rapid process from about 541 to T c, where the a axis contracts. Using a modified Bragg–Williams model, a good fit was obtained for the normalized intensities (that is, normalized, NI1/2) for the (113) and (211) reflections in $R{\overline{3}} c\hbox {\,NaNO}_{3},$ and indicates a second-order transition. Using the same model, a reasonable fit was obtained for the order parameter, S, and also supports a second-order transition.  相似文献   

3.
Property and behaviour of sand–pile interface are crucial to shaft resistance of piles. Dilation or contraction of the interface soil induces change in normal stress, which in turn influences the shear stress mobilised at the interface. Although previous studies have demonstrated this mechanism by laboratory tests and numerical simulations, the interface responses are not analysed systematically in terms of soil state (i.e. density and stress level). The objective of this study is to understand and quantify any increase in normal stress of different pile–soil interfaces when they are subjected to loading and stress relief. Distinct element modelling was carried out. Input parameters and modelling procedure were verified by experimental data from laboratory element tests. Parametric simulations of shearbox tests were conducted under the constant normal stiffness, constant normal load and constant volume boundary conditions. Key parameters including initial normal stress ( $ \sigma_{{{\text{n}}0}}^{\prime } $ ), initial void ratio (e 0), normal stiffness constraining the interface and loading–unloading stress history were investigated. It is shown that mobilised stress ratio ( $ \tau /\sigma_{\text{n}}^{\prime } $ ) and normal stress increment ( $ \Updelta \sigma_{\text{n}}^{\prime } $ ) on a given interface are governed by $ \sigma_{{{\text{n}}0}}^{\prime } $ and e 0. An increase in $ \sigma_{{{\text{n}}0}}^{\prime } $ from 100 to 400 kPa leads to a 30 % reduction in $ \Updelta \sigma_{\text{n}}^{\prime } $ . An increase in e 0 from 0.18 to 0.30 reduces $ \Updelta \sigma_{\text{n}}^{\prime } $ by more than 90 %, and therefore, shaft resistance is much lower for piles in loose sands. A unique relationship between $ \Updelta \sigma_{\text{n}}^{\prime } $ and normal stiffness is established for different soil states. It can be applied to assess the shaft resistance of piles in soils with different densities and subjected to loading and stress relief. Fairly good agreement is obtained between the calculated shaft resistance based on the proposed relationship and the measured results in centrifuge model tests.  相似文献   

4.
In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO2 and ZrO2; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO2 contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO2 contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO2 concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO2 in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.  相似文献   

5.
The textures of minerals in volcanic and plutonic rocks testify to a complexity of processes in their formation that is at odds with simple geochemical models of igneous differentiation. Zoning in plagioclase feldspar is a case in point. Very slow diffusion of the major components in plagioclase means that textural evidence for complex magmatic evolution is preserved, almost without modification. Consequently, plagioclase affords considerable insight into the processes by which magmas accumulate in the crust prior to their eventual eruption or solidification. Here, we use the example of the 1980–1986 eruptions of Mount St. Helens to explore the causes of textural complexity in plagioclase and associated trapped melt inclusions. Textures of individual crystals are consistent with multiple heating and cooling events; changes in total pressure (P) or volatile pressure ( $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O ) are less easy to assess from textures alone. We show that by allying textural and chemical analyses of plagioclase and melt inclusions, including volatiles (H2O, CO2) and slow-diffusing trace elements (Sr, Ba), to published experimental studies of Mount St. Helens magmas, it is possible to disambiguate the roles of pressure and temperature to reconstruct magmatic evolutionary pathways through temperature–pressure–melt fraction (T– $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O –F) space. Our modeled crystals indicate that (1) crystallization starts at $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  > 300 MPa, consistent with prior estimates from melt inclusion volatile contents, (2) crystal cores grow at $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  = 200–280 MPa at F = 0.65–0.7, (3) crystals are transferred to $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  = 100–130 MPa (often accompanied by 10–20 °C of heating), where they grow albitic rims of varying thicknesses, and (4) the last stage of crystallization occurs after minor heating at $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  ~ 100 MPa to produce characteristic rim compositions of An50. We hypothesize that modeled $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O decreases in excess of ~50 MPa most likely represent upward transport through the magmatic system. Small variations in modeled $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O , in contrast, can be effected by fluxing the reservoir with CO2-rich vapors that are either released from deeper in the system or transported with the recharge magma. Temperature fluctuations of 20–40 °C, on the other hand, are an inevitable consequence of incremental, or pulsed, assembly of crustal magma bodies wherein each pulse interacts with ancestral, stored magmas. We venture that this “petrological cannibalism” accounts for much of the plagioclase zoning and textural complexity seen not only at Mount St. Helens but also at arc magmas generally. More broadly we suggest that the magma reservoir below Mount St. Helens is dominated by crystal mush and fed by frequent inputs of hotter, but compositionally similar, magma, coupled with episodes of magma ascent from one storage region to another. This view both accords with other independent constraints on the subvolcanic system at Mount St. Helens and supports an emerging view of many active magmatic systems as dominantly super-solidus, rather than subliquidus, bodies.  相似文献   

6.
Single crystals of two novel calcium oxotellurate(IV) nitrates were grown under hydrothermal conditions and were structurally characterized by X-ray diffraction. Ca $_5$ Te $_4\text {O}_{12}$ (NO $_3$ ) $_2$ (H $_2$ O) $_2$ [ $Cc$ , $Z=4$ , $a=25.258(3)$ Å, $b=5.7289(7)$ Å, $c=17.0066(19)$ Å, $\beta =124.377(2)^{\circ}$ , $R[F^2 > 2\sigma (F^2)]=0.043$ , 4083 $F^2$ data, 281 parameters] can be described as a non-classic order/disorder (OD) structure, which fulfills the basic principle of OD theory, viz. local equivalence of polytypes, but does not strictly follow the vicinity condition (VC) of OD theory. The structure is made up from an alternating stacking of non-polar layers composed of isolated [TeO $_3$ ] units and Ca $^{2+}$ ions and polar layers containing NO $_3^-$ ions and water molecules. The electron lone-pairs of the [TeO $_3$ ] units protrude into the free space of the anion/water layers. The crystal under investigation was a non-classic OD-twin of domains of a maximum degree of order (MDO). At the twin plane a fragment of the second MDO polytype is located. The main building blocks of Ca $_6$ Te $_5\text {O}_{15}$ (NO $_3$ ) $_2$ [ $P2_1/c$ , $Z=4$ , $a=15.494(2)$ Å, $b=5.6145(7)$ Å, $c=39.338(4)$ Å, $\beta =142.480(5)^{\circ}$ , $R[F^2 > 2\sigma (F^2)]=0.043$ , 3026 $F^2$ data, 307 parameters] are isolated [TeO $_3$ ] units and Ca $^{2+}$ ions which are connected to a three-dimensional framework perforated by channels in which the N atoms of the nitrate anions are located and the electron lone-pairs of the [TeO $_3$ ] units protrude. The structure can topologically be derived from the structure of Ca $_5$ Te $_4\text {O}_{12}$ (NO $_3$ ) $_2$ (H $_2$ O) $_2$ by removing the water molecules and connecting the CaTeO $_3$ layers with additional [TeO $_3$ ] units and Ca $^{2+}$ ions.  相似文献   

7.
Magnesiowüstite, (Mg0.08Fe0.88)O, and wüstite, Fe0.94O, were compressed to ~36?GPa at ambient temperature in the diamond anvil cell (DAC) at the Advanced Light Source. X-ray diffraction patterns were taken in situ in radial geometry in order to study the evolution of crystallographic preferred orientation through the cubic-to-rhombohedral phase transition. Under uniaxial stress in the DAC, {100}c planes aligned perpendicular to the compression direction. The {100}c in cubic became { $\left\{ {10\bar 14} \right\}$ }r in rhombohedral and remained aligned perpendicular to the compression direction. However, the {101}c and {111}c planes in the cubic phase split into { ${10{\bar{1}}4}$ }r and { ${11{\bar{2}}0}$ }r, and (0001)r and { ${10{\bar{1}}1}$ }r, respectively, in the rhombohedral phase. The { ${11{\bar{2}}0}$ }r planes preferentially aligned perpendicular to the compression direction while { ${10{\bar{1}}4}$ }r oriented at a low angle to the compression direction. Similarly, { ${10{\bar{1}}1}$ }r showed a slight preference to align more closely perpendicular to the compression direction than (0001)r. This variant selection may occur because the 〈 ${10{\bar{1}}4}$ 〉r and [0001]r directions are the softer of the two sets of directions. The rhombohedral texture distortion may also be due to subsequent deformation. Indeed, polycrystal plasticity simulations indicate that for preferred { ${10{\bar{1}}4}$ }〈 ${1{\bar{2}}10}$ 〉r and { ${11{\bar{2}}0}$ }〈 ${{\bar{1}}101}$ 〉r slip and slightly less active { ${10{\bar{1}}1}$ }〈 ${{\bar{1}}2{\bar{1}}0}$ 〉r slip, the observed texture pattern can be obtained.  相似文献   

8.
Spectral ratios of teleseismic P waves for 15 deep (>200 km) earthquakes recorded at 146 High-Sensitivity Seismographic Network stations in the Kanto district and its surrounding area, eastern Japan, were inverted for attenuation parameter $ t_P^{ * } $ . The dataset consisted of good-quality vertical-component seismograms, whose P phases were handpicked. The P wave spectral ratios with high signal-to-noise ratios were calculated up to 1 Hz for all the station pairs, linear regressed, and then inverted for $ t_P^{ * } $ using the technique of least squares . The result showed that the active volcanic areas were clearly characterized by high $ t_P^{ * } $ . In contrast, $ t_P^{ * } $ varied in the nonvolcanic areas. The present result on the $ t_P^{ * } $ distribution was roughly consistent with the shallow part (<30 km) of an attenuation structure, which has been previously obtained based on 3-D tomography by using records of high-frequency (around 5 Hz) P waves from local earthquakes. This suggested that the present method of $ t_P^{ * } $ estimation is valid. The advantage and possible application to other areas were also discussed.  相似文献   

9.
To determine depth dependence of permeability in various geologic deposits, exponential models have often been proposed. However, spatial variability in hydraulic conductivity, K, rarely fits this trend in coarse alluvial aquifers, where complex stratigraphic sequences follow unique trends due to depositional and post-depositional processes. This paper analyzes K of alluvial-fan gravel deposits in several boreholes, and finds exponential decay in K with depth. Relatively undisturbed gravel cores obtained in the Toyohira River alluvial fan, Sapporo, Japan, are categorized by four levels of fine-sediment packing between gravel grains. Grain size is also analyzed in cores from two boreholes in the mid-fan and one in the fan-toe. Profiles of estimated conductivity, $ \overline{K} $ , are constructed from profiles of core properties through a well-defined relation between slug-test results and core properties. Errors in $ \overline{K} $ are eliminated by a moving-average method, and regression analysis provides the decay exponents of $ \overline{K} $ with depth. Moving-average results show a similar decreasing trend in only the mid-fan above ～30-m depth, and the decay exponent is estimated as ≈0.11 m?1, which is 10- to 1,000-fold that in consolidated rocks. A longitudinal cross section is also generated by using the profiles to establish hydrogeologic boundaries in the fan.  相似文献   

10.
The effectiveness of transmitting underground water in rock fractures is strongly influenced by the widths of the fractures and their interconnections. However, the geometries needed for water flow in fractured rock are also heavily controlled by the confining pressure conditions. This paper is intended to study the seepage properties of fractured rocks under different confining pressures. In order to do this, we designed and manufactured a water flow apparatus that can be connected to the electro-hydraulic servo-controlled test system MTS815.02, which provides loading and exhibits external pressures in the test. Using this apparatus, we tested fractured mudstone, limestone and sandstone specimens and obtained the relationship between seepage properties and variations in confining pressure. The calculation of the seepage properties based on the collection of water flow and confining pressure differences is specifically influenced by non-Darcy flow. The results show that: (1) The seepage properties of fractured rocks are related to confining pressure, i.e. with the increase of confining pressure, the permeability $ k $ decreases and the absolute value of non-Darcy flow coefficient $ \beta $ increases. (2) The sandstone coefficients $ k $ and $ \beta $ range from $ 1.03 \times 10^{ - 18} $ to $ 1.53 \times 10^{ - 17} $  m2 and $ - 1.13 \times 10^{17} $ to $ - 2.35 \times 10^{18} $  m?1, respectively, and exhibit a greater change compared to coefficients of mudstone and limestone. (3) From the regression analysis of experimental data, it is concluded that the polynomial function is a better fit than the power and logarithmic functions. The results obtained can provide an important reference for understanding the stability of rock surrounding roadways toward prevention of underground water gushing-out, and for developing underground resources (e.g. coal).  相似文献   

11.
A new experimental model has been designed to simulate the influence of a natural fracture network on the propagation geometry of hydraulic fractures in naturally fractured formations using a tri-axial fracturing system. In this model, a parallel and symmetrical pre-fracture network was created by placing cement plates in a cubic mold and filling the mold with additional cement to create the final testing block. The surface of the plates will thus be weakly cemented and form pre-fractures. The dimension and direction of the pre-fractures can be controlled using the plates. The experiments showed that the horizontal differential stress $\Updelta \sigma$ and the angle $\Updelta \theta$ between the maximum horizontal principal in situ stress and the pre-fracture are the dominating factors for the initiation and propagation of hydraulic fractures. For $\Updelta \theta = 90^\circ$ and $\Updelta \sigma \ge 2{\text{ MPa}}$ or $\Updelta \theta = 60^\circ$ and $\Updelta \sigma \ge 4{\text{ MPa}}$ , the direction of the initiation and propagation of the hydraulic fractures are consistent with or deviate from the normal direction of the pre-fracture. When the hydraulic fractures approach the pre-fractures, the direction of the hydraulic fracture propagation will be consistent with the normal direction of the pre-fracture. Otherwise, the hydraulic fracture will deflect and perpendicularly cross the parallel and symmetric pre-fracture network. For $\Updelta \theta = 90^\circ$ and $\Updelta \sigma < 2{\text{ MPa}},\,\Updelta \theta = 60^\circ$ , and $\Updelta \sigma < 4{\text{ MPa}}$ or $\Updelta \theta = 45^\circ$ and $\Updelta \sigma = 4 - 8{\text{ MPa}}$ , before the hydraulic fracture and the pre-fractures intersect, the direction of the hydraulic fracture propagation remains unchanged, and the pre-fractures open or dilate when the hydraulic fracture propagates to the intersection point, forming a complicated hydraulic fracture network with the propagation region of the overall hydraulic fracture network taking the shape of an ellipse. In this condition, the complexity level of the hydraulic fracture is controlled by the net pressure, the compressive normal stress acting on the pre-fractures, the shearing strength and the cohesion strength of the planes of weakness. The conclusions of this research are inconsistent with the formulation of the approach angle that has been widely accepted by previous studies. The principle of hydraulic fracture propagation is that it follows the least resistance, the most preferential propagation, and the shortest propagation path.  相似文献   

12.
Gas chromatography, palynomorph constituents, and maturation are analyzed for oil samples of the Campanian Khasib and Tannuma Formations in the wells of East Baghdad oil field for biomarker studies, while palynomorph constituents and their maturation, Rock Eval pyrolysis, total organic carbon (TOC) analysis are carried on for the Upper Jurassic and the Cretaceous Formations of core samples from the same wells for dating and evaluation of the source rocks. The gas chromatography of these oils have shown biomarkers of abundant ranges of n-alkanes of less than C22(C17–C21) with C19 and C18 peaks to suggest mainly liquid oil constituents of paraffinic hydrocarbons from marine algal source of restricted palaeoenvironments in the reservoir as well as low nonaromatic $ {\hbox{C}}_{15}^{+} $ peaks to indicate their slight degradation and water washing. Oil biomarkers of $ \Pr ./{\hbox{Ph}}{.} = {0}{.85,}{{\hbox{C}}_{31}}/{{\hbox{C}}_{30}} < 1.0 $ , location is in the triangle of C27–C29 sterane, C28/C29 of 0.6 sterane, oleanane of 0.01, and CPI = 1.0, could indicate anoxic marine environment with carbonate deposition of Upper Jurassic–Early Cretaceous source. The recorded palynomorph constituents in this oil and associated water are four miospore, seven dinoflagellates, and one Tasmanite species that could confirm affinity to the Upper most Jurassic–Lower Cretaceous Chia Gara and Ratawi Formations. The recorded palynomorphs from the reservoir oil (Khasib and Tannuma Formations) are of light brown color of $ {\hbox{TAI}} = 2.8 - 3.0 $ and comparable to the mature palynomorphs that belong to Chia Gara and Lower part of Ratawi Formations. Chia Gara Formation had generated and expelled high quantity of oil hydrocarbons according their TOC weight percent of 0.5–8.5 with ${S_2} = 2.5 - 18.5\,{\hbox{mg}}\,{\hbox{Hc/g}}\;{\hbox{rock}} $ , high hydrogen index of the range 150–450 mg Hc/g Rock, good petroleum potential of 4.5–23.5 mg Hc/g rock, mature ( $ {\hbox{TAI}} = 2.8 - 3.0 $ and $ {\hbox{T}}\max = 428 - 443{\hbox{C}} $ ), kerogen type II, and palynofacies parameters of up to 100 amorphous organic matters with algae deposited in dysoxic–anoxic to suboxic–anoxic basin, while the palynomorphs of the rocks of Khasib Formation are of amber yellow color of TAI = 2.0 with low TOC and hence not generated hydrocarbons. But, this last formation could be considered as oil reservoir only according their high porosity (15–23%) and permeability (20–45 mD) carbonate rocks with structural anticline closure trending NW-SE. That oil have generated and expelled during two phases; the first is during Early Palaeogene that accumulated in traps of the Cretaceous structural deformation, while the second is during Late Neogene’s.  相似文献   

13.
In-situ powder diffraction measurements between 90 and 935?K on four anorthite-rich plagioclase samples (An100, An96Ab4, An89Ab11 and An78Ab22) were used to determine the detailed evolution of these samples through the $I \overline{1} $ – $P \overline{1} $ phase transition. The c-type reflections indicative of $P \overline{1} $ symmetry were detected only in An100, An96Ab4, whereas deviations in the evolution of the unit-cell parameters with temperature were observed in all samples, most prominently in the β unit-cell angle. The c-type reflections disappear at ~510 and ~425?K in An100 and An96Ab4 respectively, and their intensity decreases according to a tricritical trend $ I^{2} \propto \left( {T - T_{\text{c}} } \right) $ . The cell parameter changes were used to determine the spontaneous strains arising from the transition which were modelled with Landau theory, allowing for low-temperature quantum saturation, in order to determine the thermodynamic behaviour. In An100 tricritical behaviour was observed [T c?=?512.7(4)?K; θs?=?394(4)] in good agreement with previous studies, and the c-type superlattice reflections indicative of $P \overline{1} $ symmetry persist up to the T c determined from the spontaneous strain, and then disappear. The evolution of the spontaneous strain in An96Ab4 is tricritical at low temperatures [T c?=?459(1) K, θs?=?396(5)] up to the temperature of disappearance of c-type reflections, but becomes second order beyond ~440?K. In An89Ab11 the strain displays second-order behaviour throughout [T c?=?500(1) and θs?=?212(5)], and the c-type reflections are not detected in the powder diffraction patterns at any temperature. The apparent discrepancy between the absence of c-type reflections in temperature ranges where the cell parameters display significant spontaneous strain is resolved through consideration of the sizes of the anti-phase domains within the crystals. It is deduced that the tricritical phase transition occurs in well-ordered crystals with large domains in which the behavior of individual domains is dominant (i.e. in pure anorthite) or where the $P \overline{1} $ distortions within the domains are large enough to dominate the structural coherency strains between the domains. When both the magnitude of the $P \overline{1} $ pattern of displacements of the tetrahedral framework become smaller and the influence of the structural coherency between anti-phase domains becomes significant, the thermodynamic behavior becomes 2nd-order in character, the c-type reflections disappear, and the orientation of the spontaneous strain changes.  相似文献   

14.
Natural springs have been reliable sources of domestic water and have allowed for the development of recreational facilities and resorts in the Central Appalachians. The structural history of this area is complex and it is unknown whether these natural springs receive significant recharge from modern precipitation or whether they discharge old water recharged over geological times scales. The main objective of this study was to use stable isotopes of water ( $\delta^{18} {\text{O}}_{{{\text{H}}_{2} {\text{O}}}}$ and $\delta^{2} {\text{H}}_{{{\text{H}}_{2} {\text{O}}}}$ ), dissolved inorganic carbon ( $\delta^{13} {\text{C}}_{\text{DIC}}$ ) and dissolved sulfate ( $\delta^{34} {\text{S}}_{{{\text{SO}}_{4} }}$ and $\delta^{18} {\text{O}}_{{{\text{SO}}_{4} }}$ ) to delineate sources of water, carbon and sulfur in several natural springs of the region. Our preliminary isotope data indicate that all springs are being recharged by modern precipitation. The oxygen isotope composition indicates that waters in thermal springs did not encounter the high temperatures required for O isotope exchange between the water and silicate/carbonate minerals, and/or the residence time of water in the aquifers was short due to high flow rates. The carbon isotopic composition of dissolved inorganic carbon and sulfur/oxygen isotopic composition of dissolved sulfate provide evidence of low-temperature water–rock interactions and various biogeochemical transformations these waters have undergone along their flow path.  相似文献   

15.
A detailed hydrogeochemical study of groundwater in the Cecina coastal plain (Livorno province, Italy) and its inner sectors was undertaken in 2008, as chemical analyses carried out on groundwater since 2006 have revealed Cr(VI) concentrations of up to 49 μg/L (well above the permissible limit of 5 μg/L). Ophiolite outcrops are present throughout the study area, and their fragments likely represent a significant portion of the existing multilayered aquifer skeleton. Waters delivered by the serpentinite outcrops have a typically Mg–HCO3 composition, whereas those of the coastal plain are prevailingly of the Ca/Mg–HCO3 type with significant Mg contents. Significant NO3 contamination characterises the studied coastal plain, and an interesting negative correlation exists between Cr(VI) and both NO3 and SO4 deriving from the widespread use of (NH4)2SO4 as a farm fertilizer. Chromium speciation calculations carried out using the EQ3NR code reveal that the prevailing Cr(VI) species in solution is CrO4 2?; however, CaCrO4° and MgCrO4° neutral complexes represent significant percentages (up to 42 %). These findings suggest that the mobility and consequently the bioavailability of Cr(VI) can be significantly enhanced by these neutral complexes, which are not considered to be affected by adsorption/desorption processes. The Cr(VI) source, investigated by means of the Mg/SiO2 molar ratio, seems to be represented mainly by Mg-bearing minerals of the chlorite group. Petrographic observations confirm the occurrence of this mineral group. The interaction between rainwater and the local serpentinite rock was simulated at different $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ conditions by reaction path modelling using the EQ3/6 software package. $P_{{{\text{O}}_{ 2} }}$ was varied in accordance with the assumption that redox conditions are determined in part by NO3. Results are in good agreement with experimental data on spring waters and subordinately with data on some coastal plain groundwater, which plot in a rather wide $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ field. Although the dissolved Cr content is mostly of natural origin, fertilization may affect its fate.  相似文献   

16.
This study presents accurate and precise iron isotopic data for 16 co-magmatic rocks and 6 pyroxene–magnetite pairs from the classic, tholeiitic Red Hill sill in southern Tasmania. The intrusion exhibits a vertical continuum of compositions created by in situ fractional crystallisation of a single injection of magma in a closed igneous system and, as such, constitutes a natural laboratory amenable to determining the causes of Fe isotope fractionation in magmatic rocks. Early fractionation of pyroxenes and plagioclase, under conditions closed to oxygen exchange, gives rise to an iron enrichment trend and an increase in $ f_{{{\text{O}}_{2} }} $ of the melt relative to the Fayalite–Magnetite–Quartz (FMQ) buffer. Enrichment in Fe3+/ΣFemelt is mirrored by δ57Fe, where VIFe2+-bearing pyroxenes partition 57Fe-depleted iron, defining an equilibrium pyroxene-melt fractionation factor of $ \Updelta^{57} {\text{Fe}}_{{{\text{px}} - {\text{melt}}}} \le - 0.25\,\permille \times 10^{6} /T^{2} $ . Upon magnetite saturation, the $ f_{{{\text{O}}_{2} }} $ and δ57Fe of the melt fall, commensurate with the sequestration of the oxidised, 57Fe-enriched iron into magnetite, quantified as $ \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{melt}}}} = + 0.20\,\permille \times 10^{6} /T^{2} $ . Pyroxene–magnetite pairs reveal an equilibrium fractionation factor of $ \Updelta^{57} {\text{Fe}}_{{{\text{mtn}} - {\text{px}}}} \approx + 0.30\,\permille $ at 900–1,000?°C. Iron isotopes in differentiated magmas suggest that they may act as an indicator of their oxidation state and tectonic setting.  相似文献   

17.
Precious metals accompany all types of epithermal deposits. In general, the largest of these deposits occur in intrusive or extrusive rocks of alkaline or calc-alkaline affinity. The Apigania Bay vein system and Au–Ag mineralization is hosted in Mesozoic marbles and schists, and is composed primarily of five nearly parallel, high-angle quartz veins that extend for at least 200 m. Gold–silver mineralization, in association with more than thirty ore and vein minerals, is developed in three stages and occurs at the contact of marbles and schists. Zones of epidote–chlorite–calcite and sericite–albite alteration are associated with precious metal-bearing milky and clear quartz veins. Fluid inclusion studies suggest that hydrothermal mineralization was deposited under hydrostatic pressures of ~100 bars, at temperature of 120–235°C, from low to moderate, calcium-bearing, saline fluids of 0.2 to 6.8 equiv. wt.% NaCl. Calculated isotope compositions (δ18O?=??4.7‰ to 1.7‰ and δD?=??120‰ to ?80‰) for waters in equilibrium with milky and clear quartz are consistent with mixing with dilute, low temperature meteoric ore fluids. Calculated δ 13CCO2 (0.6‰ to 1.1‰) and δ 34SH2S (?7.3 to ?0.3‰) compositions of the ore fluids indicate exchange, in an open system, with a metasedimentary source. Gold and silver deposition was associated with degassing of hydrogen due to intense uplift of the mineralizing area. The physicochemical conditions of mineralization stages I to III range between 200°C and 150°C, $f_{{\text{S}}_2 } = 10^{ - 18.1} $ to 10?16.8, $f_{{\text{O}}_2 } = 10^{ - 44.0} $ to 10?41.5, pH?=?6.9 to7.6, $f_{{\text{H}}_{\text{2}} {\text{S}}} = 10^{ - 3.4} $ to 10?2.6 and $a_{{\text{H}}_{\text{2}} {\text{S}}} = 10^{ - 2.7} $ to 10?2.6. Apigania Bay could be possibly considered the latest evolutional phase of Tinos hydrothermal system.  相似文献   

18.
The flow rule used in the high-cycle accumulation (HCA) model proposed by Niemunis et al. (Comput Geotech 32: 245, 2005) is examined on the basis of the data from approximately 350 drained long-term cyclic triaxial tests (N = 105 cycles) performed on 22 different grain-size distribution curves of a clean quartz sand. In accordance with (Wichtmann et al. in Acta Geotechnica 1: 59, 2006), for all tested materials, the “high-cyclic flow rule (HCFR)”, i.e., the ratio of the volumetric and deviatoric strain accumulation rates \(\dot{\varepsilon}_{\rm{v}}^{{\rm acc}}/\dot{\varepsilon}_{\rm{q}}^{{\rm acc}}\) , was found dependent primarily on the average stress ratio η av = q av/p av and independent of amplitude, soil density and average mean pressure. The experimental HCFR can be fairly well approximated by the flow rule of the modified Cam-clay (MCC) model. Instead of the critical friction angle \(\varphi_{\rm{c}}\) which enters the flow rule for monotonic loading, the HCA model uses the MCC flow rule expression with a slightly different parameter \(\varphi_{\rm{cc}}\) . It should be determined from cyclic tests. \(\varphi_{\rm{cc}}\) and \(\varphi_{\rm{c}}\) are of similar magnitude but not always identical, because they are calibrated from different types of tests. For a simplified calibration in the absence of cyclic test data, \(\varphi_{\rm{cc}}\) may be estimated from the angle of repose \(\varphi_{\rm{r}}\) determined from a pluviated cone of sand (Wichtmann et al. in Acta Geotechnica 1: 59, 2006). However, the paper demonstrates that the MCC flow rule with \(\varphi_{\rm{r}}\) does not fit well the experimentally observed HCFR in the case of coarse or well-graded sands. For an improved simplified calibration procedure, correlations between \(\varphi_{\rm{cc}}\) and parameters of the grain-size distribution curve (d 50,   C u) have been developed on the basis of the present data set. The approximation of the experimental HCFR by the generalized flow rule equations proposed in (Wichtmann et al. in J Geotech Geoenviron Eng ASCE 136: 728, 2010), considering anisotropy, is also discussed in the paper.  相似文献   

19.
Groundwater-level data from an aquifer test utilizing four pumped wells conducted in the South Pasco wellfield in Pasco County, Florida, USA, were analyzed to determine the anisotropic transmissivity tensor, storativity, and leakance in the vicinity of the wellfield. A weighted least-squares procedure was used to analyze drawdowns measured at eight observation wells, and it was determined that the major axis of transmissivity extends approximately from north to south and the minor axis extends approximately from west to east with an angle of anisotropy equal to N4.54°W. The transmissivity along the major axis ${\left( {T_{{\xi \xi }} } \right)}$ is 14,019 m2 day–1, and the transmissivity along the minor axis ${\left( {T_{{\eta \eta }} } \right)}$ is 4,303 m2 day–1. The equivalent transmissivity $T_{e} = {\left( {T_{{\xi \xi }} T_{{\eta \eta }} } \right)}^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} = 7,767{{\text{m}}^{2} } \mathord{\left/ {\vphantom {{{\text{m}}^{2} } {{\text{day}}^{{ - {\text{1}}}} }}} \right. \kern-0em} {{\text{day}}^{{ - {\text{1}}}} }$ , and the ratio of anisotropy is 3.26. The storativity of the aquifer is 7.52?×?10?4, and the leakance of the overlying confining unit is 1.37?×?10?4 day?1. The anisotropic properties determined for the South Pasco wellfield in this investigation confirm the results of previous aquifer tests conducted in the wellfield and help to quantify the NW–SE to NE–SW trends for regional fracture patterns and inferred solution-enhanced flow zones in west-central Florida.  相似文献   

20.
Electron paramagnetic resonance (EPR) study of single crystals of forsterite co-doped with chromium and scandium has revealed, apart from the known paramagnetic centers Cr3+(M1) and Cr3+(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) (Ryabov in Phys Chem Miner 38:177–184, 2011), a new center Cr3+(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc3+ formed by a Cr3+ ion substituting for Mg2+ at the M1 structural position with a nearest-neighbor Mg2+ vacancy at the M2 position and a Sc3+ ion presumably at the nearest-neighbor M1 position. For this center, the conventional zero-field splitting parameters D and E and the principal g values have been determined as follows: D?=?33,172(29) MHz, E?=?8,482(13) MHz, g?=?[1.9808(2), 1.9778(2), 1.9739(2)]. The center has been compared with the known ion pair Cr3+(M1)–Al3+ (Bershov et al. in Phys Chem Miner 9:95–101, 1983), for which the refined EPR data have been obtained. Based on these data, the known sharp M1″ line at 13,967?cm?1 (with the splitting of 1.8?cm?1), observed in low-temperature luminescence spectra of chromium-doped forsterite crystals (Glynn et al. in J Lumin 48, 49:541–544, 1991), has been ascribed to the Cr3+(M1)–Al3+ center. It has been found that the concentration of the new center increases from 0 up to 4.4?×?1015?mg?1, whereas that of the Cr3+(M1) and Cr3+(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) centers quickly decreases from 7.4?×?1015?mg?1 down to 3?×?1015?mg?1 and from 2.7?×?1015?mg?1 down to 0.5?×?1015?mg?1, i.e., by a factor of 2.5 and 5.4, respectively, with an increase of the Sc content from 0 up to 0.22 wt?% (at the same Cr content 0.25 wt?%) in the melt. When the Sc content exceeds that of Cr, the concentration of the new center decreases most likely due to the formation of the Sc3+(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc3+ complex instead of the Cr3+(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc3+ center. The formation of such ordered neutral complex is in agreement with the experimental results, concerning the incorporation of Sc into olivine, recently obtained by Grant and Wood (Geochim Cosmochim Acta 74:2412–2428, 2010).  相似文献   

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