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1.
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   

2.
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   

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.
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   

5.
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   

6.
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   

7.
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   

8.
In elastic media, finite-difference (FD) implementations of free-surface (FS) boundary conditions on partly staggered grid (PSG) use the highly dispersive vacuum formulation (VPSG). The FS boundary is embedded into a “vacuum” grid layer (null Lame’s constants and negligible density values) where the discretized equations of motion allow computing surface displacements. We place a new set of compound (stress-displacement) nodes along a planar FS and use unilateral mimetic FD discretization of the zero-traction conditions for displacement computation (MPSG). At interior nodes, MPSG reduces to standard VPSG methods and applies fourth-order centered FD along cell diagonals for staggered differentiation combined with nodal second-order FD in time. We perform a dispersion analysis of these methods on a Lamb’s problem and estimate dispersion curves from the phase difference of windowed numerical Rayleigh pulses at two FS receivers. For a given grid sampling criterion (e.g., six or ten nodes per reference S wavelength λ S), MPSG dispersion errors are only a quarter of the VPSG method. We also quantify root-mean-square (RMS) misfits of numerical time series relative to analytical waveforms. MPSG RMS misfits barely exceed 10 % when nine nodes sample the minimum S wavelength $\lambda _{\text {MIN}}^{\mathrm {S}}$ in transit (along distances $\sim $ 145 $\lambda _{\text {MIN}}^{\mathrm {S}}$ ). In same tests, VPSG RMS misfits exceed 70 %. We additionally compare MPSG to a consistently fourth-order mimetic method designed on a standard staggered grid. The latter equates the former’s dispersion errors on grids twice denser and shows higher RMS precision only on grids with six or less nodes per $\lambda _{\text {MIN}}^{\mathrm {S}}$ .  相似文献   

9.
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   

10.
Several new radiation defects with total electron spin S?=?1 occurring in electron-irradiated, synthetic ??-quartz have been observed by using electron paramagnetic resonance spectroscopy. These defects are considered to be biradicals, i.e., pairs of S?=?1/2 species. The concentration of these centers depends on the condition of the fast-electron irradiation. They have different decay behaviors that allow measurements of any individual species especially when it predominates over the others. The primary spin Hamiltonian parameter matrices g 1, g 2, D have now been determined for two similar defects, which herein are labeled $ E_{2}^{\prime \prime } $ and $ E_{4}^{\prime \prime } $ . Inter-electron distances estimated by using the magnetic dipole model, suggest that the structures of centers $ E_{2}^{\prime \prime } $ and $ E_{4}^{\prime \prime } $ both involve the unpaired electrons each located in orbitals of two silicon atoms next to a common oxygen vacancy but which have slightly different Si?CSi distances at 0.90 and 0.79?nm, respectively. This model is consistent with previous DFT calculations of the triplet configurations with local energetic minima. Observed decay behaviors suggest a transformation of centers $ E_{2,4}^{\prime \prime } $ to the analogous $ E_{1}^{\prime \prime } $ center. These triplet centers in quartz provide new insights into the structures of analogous defects in amorphous silica.  相似文献   

11.
Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO2 whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ13CTDIC (total dissolved inorganic carbon) on various spatiotemporal scales in the unsaturated and saturated zones of volcanic flows of the Argnat basin (French Massif Central) have been carried out to identify the carbon sources in the system. Mantellic sources are related to faults promoting CO2 uplift from the mantle to the saturated zone. The contribution of this source is counterbalanced by infiltration of water through the unsaturated zone, accompanied by dissolution of soil CO2 or even atmospheric CO2 during cold periods. Monitoring and modeling of δ13CTDIC in the unsaturated zone shows that both $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ13CTDIC are controlled by air temperature which influences soil respiration and soil-atmosphere CO2 exchanges. The internal geometry of volcanic lava flows controls water patterns from the unsaturated zone to saturated zone and thus may explain δ13C heterogeneity in the saturated zone at the basin scale.  相似文献   

12.
Sr- and Ca-rich waylandite, $ {\left( {{\hbox{B}}{{\hbox{i}}_{0.{54}}}{\hbox{S}}{{\hbox{r}}_{0.{31}}}{\hbox{C}}{{\hbox{a}}_{0.{25}}}{{\hbox{K}}_{0.0{1}}}{\hbox{B}}{{\hbox{a}}_{0.0{1}}}} \right)_{\Sigma 1.12}}{{\hbox{H}}_{0.{18}}}{\left( {{\hbox{A}}{{\hbox{l}}_{{2}.{96}}}{\hbox{C}}{{\hbox{u}}_{0.0{2}}}} \right)_{\Sigma 2.98}}{\left[ {{{\left( {{{\hbox{P}}_{0.{97}}}{{\hbox{S}}_{0.0{3}}}{\hbox{S}}{{\hbox{i}}_{0.0{1}}}} \right)}_{\Sigma 1.00}}{{\hbox{O}}_4}} \right]_2}{\left( {\hbox{OH}} \right)_6} $ , from Wheal Remfry, Cornwall, United Kingdom has been investigated by single-crystal X-ray diffraction and electron microprobe analyses. Waylandite crystallises in space group R $ \overline 3 $ ? m, with the cell parameters: a?=?7.0059(7) Å, c?=?16.3431(12) Å and V?=?694.69(11) Å3. The crystal structure has been refined to R 1?=?3.76%. Waylandite has an alunite-type structure comprised of a rhombohedral stacking of (001) composite layers of corner-shared AlO6 octahedra and PO4 tetrahedra, with (Bi,Sr,Ca) atoms occupying icosahedrally coordinated sites between the layers.  相似文献   

13.
The Gibbs free energy and volume changes attendant upon hydration of cordierites in the system magnesian cordierite-water have been extracted from the published high pressure experimental data at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =P total, assuming an ideal one site model for H2O in cordierite. Incorporating the dependence of ΔG and ΔV on temperature, which was found to be linear within the experimental conditions of 500°–1,000°C and 1–10,000 bars, the relation between the water content of cordierite and P, T and \(f_{{\text{H}}_{\text{2}} {\text{O}}} \) has been formulated as $$\begin{gathered} X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} = \hfill \\ \frac{{f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }}{{\left[ {{\text{exp}}\frac{1}{{RT}}\left\{ {64,775 - 32.26T + G_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{1, }}T} - P\left( {9 \times 10^{ - 4} T - 0.5142} \right)} \right\}} \right] + f_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{P, T}}} }} \hfill \\ \end{gathered} $$ The equation can be used to compute H2O in cordierites at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) <1. Our results at different P, T and partial pressure of water, assuming ideal mixing of H2O and CO2 in the vapour phase, are in very good agreement with the experimental data of Johannes and Schreyer (1977, 1981). Applying the formulation to determine \(X_{{\text{H}}_{\text{2}} {\text{O}}}^{{\text{crd}}} \) in the garnet-cordierite-sillimanite-plagioclase-quartz granulites of Finnish Lapland as a test case, good agreement with the gravimetrically determined water contents of cordierite was obtained. Pressure estimates, from a thermodynamic modelling of the Fe-cordierite — almandine — sillimanite — quartz equilibrium at \(P_{{\text{H}}_{\text{2}} {\text{O}}} = 0\) and \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =Ptotal, for assemblages from South India, Scottish Caledonides, Daly Bay and Hara Lake areas are compatible with those derived from the garnetplagioclase-sillimanite-quartz geobarometer.  相似文献   

14.
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   

15.
The thermodynamic calculation of dehydration reacton suggests very low activity of H2O during metamorphic peak of the Archaean granulite complex in the region studied.The αH2O values for Al-rich gneiss and hypersthene biotite gneiss-granulite in the Taipingzhai region are usually between 0.10 and 0.20,and those in the Louzishan region are 0.15-0.25.The fugacity of O2 in terms of lgf O2 in whole region ranges form-8to-14.The average coefficients of (δμH2O/δHMg^Bt)and(δμO2/δXMg^Bt)in the Taipingzhai region are-0.293 and-1.60 respectively,and those in the Louzishan region are-0.364and-1.420.The activity of H2O is very low in the whole region,but its values and other data mentioned above are considerably constant from place to place within a given region,even in rocks of dirrerent lithological characters.However,they show a certain gradient between different regions.Such characteristics are compatible with the genetic mechanism known as“carbonic metamorphism” put forward by Newton et al.,i.e.,the α H2O during the peak stage is controlled by permeation of pervasive CO2 influx of the mantle source,and shows features of external buffering.  相似文献   

16.
The biotite zone assemblage: calcite-quartz-plagioclase (An25)-phengite-paragonite-chlorite-graphite, is developed at the contact between a carbonate and a pelite from British Columbia. Thermochemical data for the equilibrium paragonite+calcite+2 quartz=albite+ anorthite+CO2+H2O yields: $$\log f{\text{H}}_{\text{2}} {\text{O}} + \log f{\text{CO}}_{\text{2}} = 5.76 + 0.117 \times 10^{ - 3} (P - 1)$$ for a temperature of 700°K and a plagioclase composition of An25. By combining this equation with equations describing equilibria between graphite and gas species in the system C-H-O, the following partial pressures: \(P{\text{H}}_2 {\text{O}} = 2572{\text{b, }}P{\text{CO}}_2 = 3162{\text{b, }}P{\text{H}}_2 = 2.5{\text{b, }}P{\text{CH}}_4 = 52.5{\text{b, }}P{\text{CO}} = 11.0{\text{b}}\) are obtained for \(f{\text{O}}_2 = 10^{ - 26}\) . If total pressure equals fluid pressure, then the total pressure during metamorphism was approximately 6 kb. The total fluid pressure calculated is extremely sensitive to the value of \(f{\text{O}}_2\) chosen.  相似文献   

17.
We present new equilibrium mixed-volatile (H2O–CO2) solubility data for a phonotephrite from Erebus volcano, Antarctica. H2O–CO2-saturated experiments were conducted at 400–700 MPa, 1,190 °C, and ~NNO + 1 in non-end-loaded piston cylinders. Equilibrium H2O–CO2 fluid compositions were determined using low-temperature vacuum manometry, and the volatile and major element compositions of the glassy run products were determined by Fourier transform infrared spectroscopy and electron microprobe. Results show that the phonotephrite used in this study will dissolve ~0.8 wt% CO2 at 700 MPa and a fluid composition of $ X_{{{\text{H}}_{ 2} {\text{O}}}} $ ~0.4, in agreement with previous experimental studies on mafic alkaline rocks. Furthermore, the dissolution of CO2 at moderate to high $ X_{{{\text{H}}_{ 2} {\text{O}}}}^{\text{fluid}} $ in our experiments exceeds that predicted using lower-pressure experiments on similar melts from the literature, suggesting a departure from Henrian behavior of volatiles in the melt at pressures above 400 MPa. With these data, we place new constraints on the modeling of Erebus melt inclusion and gas emission data and thus the interpretation of its magma plumbing system and the contributions of primitive magmas to passive and explosive degassing from the Erebus phonolite lava lake.  相似文献   

18.
Geotechnical investigation projects in Korea produced data on the in situ modulus of deformation of rock masses (E M) measured with the borehole test, rock mass rating (RMR), and Q-system. The modulus of deformation of rock masses was correlated with the degree of weathering, RMR, and Q values. Determination of E M for each degree of weathering allows for the results to be used to classify the degree of weathering or to predict E M. The relation between E M and RMR is represented by $ E_{\text{M}} = 10^{{\frac{{{\text{RMR}} - 16}}{50}}} $ , which returns values 2–3 times lower than those reported in previous studies. Despite scatter in the values, due to larger dataset used in this study, the proposed equation may be used to predict the in situ modulus of deformation from RMR values. In addition, the relation between modulus of deformation and Q values is $ E_{\text{M}} = 10^{{0.32{ \log }Q + 0.585}} $ .  相似文献   

19.
In a regional metamorphic terrain where six isograds have been mapped based on mineral reactions that are observed in metacarbonate rocks, the P-T conditions and fugacities of CO2 and H2O during metamorphism were quantified by calculations involving actual mineral compositions and experimental data. Pressure during metamorphism was near 3,500 bars. Metamorphic temperatures ranged from 380° C (biotite-chlorite isograd) to 520° C (diopside isograd). \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{CO}}_{\text{2}} }\) / \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) in general is higher in metacarbonate rocks below the zoisite isograd than in those above the zoisite isograd. Calculated \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) are consistent with carbonate rocks above the zoisite isograd having equilibrated during metamorphism with a bulk supercritical fluid in which \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) = P total. Calculations indicate that below the zoisite isograd, however, \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) was less than Ptotal, and that this condition is not due to the presence of significant amounts of species other than CO2 and H2O in the system C-O-H-S. Calculated \(P_{{\text{CO}}_{\text{2}} }\) /( \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) ) is low (0.06–0.32) above the zoisite isograd. The differences in conditions above and below the zoisite isograd may indicate that the formation of zoisite records the introduction of a bulk supercritical H2O-rich fluid into the metacarbonates. The results of the study indicate that \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) are constant on a thin section scale, but that gradients in \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) existed during metamorphism on both outcrop and regional scales.  相似文献   

20.
Macroscopic behavior of expansive soil is governed by surface forces rather than gravitational forces. These physicochemical surface forces can be investigated through two electromagnetic properties in response to an applied electromagnetic field as real (relative) permittivity, κ′, and effective (electrical) conductivity, σ. This paper presents the results of dielectric measurements on four natural expansive soils using 1–100 MHz electromagnetic waves in two different test setups. The equipment setup, calibration process and measurement limitations are evaluated, and the dielectric spectra, in terms of the dispersion of real permittivity/effective conductivity with frequency, are presented. A procedure is presented to quantify the thickness of a fully developed diffuse double layer (DDL). The influence of salt concentration on DDL, as well as the dielectric responses, is assessed. Two parameters of special physical meaning are defined in the article: ${\upkappa} _{{{\text{inf}}}}^{\prime }$ , representative of the dielectric response by sample mineralogy, microstructure and saturation ratio, and σdc, combining the roles assumed by both surface conduction and pore fluid conduction. Evaluation is attempted on their magnitudes at the optimum compaction state and evolutions at different one-dimensional deforming stages. Extensive analysis is performed on the roles of ${\upkappa} _{{{\text{inf}}}}^{\prime }$ and σdc on the hydration status and structural anisotropy of an oedometer sample.  相似文献   

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