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1.
The dehydroxylation reactions of chrysotile Mg3Si2O5(OH)4 and brucite Mg(OH)2 were studied under inert nitrogen atmosphere using isothermal and non-isothermal approaches. The brucite decomposition was additionally studied under CO2 in order to check the influence of a competing dehydroxylation/carbonation/decarbonisation reaction on the reaction kinetics. Isothermal experiments were conducted using in situ high-temperature X-ray powder diffraction, whereas non-isothermal experiments were performed by thermogravimetric analyses. All data were treated by model-free, isoconversional approaches (‘time to a given fraction’ and Friedman method) to avoid the influence of kinetic misinterpretation caused by model-fitting techniques. All examined reactions are characterised by a dynamic, non-constant reaction-progress-resolved (‘α’-resolved) course of the apparent activation energy E a and indicate, therefore, multi-step reaction scenarios in case of the three studied reactions. The dehydroxylation kinetics of chrysotile can be subdivided into three different stages characterised by a steadily increasing E a (α ≤ 15 %, 240–300 kJ/mol), before coming down and forming a plateau (15 % ≤ α ≤ 60 %, 300–260 kJ/mol). The reaction ends with an increasing E a (α ≥ 60 %, 260–290 kJ/mol). The dehydroxylation of brucite under nitrogen shows a less dynamic, but generally decreasing trend in E a versus α (160–110 kJ/mol). In contrast to that, the decomposition of brucite under CO2 delivers a dynamic course with a much higher apparent E a characterised by an initial stage of around 290 kJ/mol. Afterwards, the apparent E a comes down to around 250 kJ/mol at α ~ 65 % before rising up to around 400 kJ/mol. The delivered kinetic data have been investigated by the z(α) master plot and generalised time master plot methods in order to discriminate the reaction mechanism. Resulting data verify the multi-step reaction scenarios (reactions governed by more than one rate-determining step) already visible in E a versus α plots.  相似文献   

2.
Elastic behavior and pressure-induced structural evolution of synthetic boron-mullite “Al5BO9” (a = 5.678(2) Å, b = 15.015(4) Å and c = 7.700(3) Å, space group Cmc21, Z = 4) were investigated up to 7.4 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase transition or anomalous compressional behavior occurred within the investigated P range. Fitting the P–V data with a truncated second-order (in energy) Birch-Murnaghan Equation-of-State (BM-EoS), using the data weighted by the uncertainties in P and V, we obtained: V 0 = 656.4(3) Å3 and K T0 = 165(7) GPa (β V0 = 0.0061(3) GPa?1). The evolution of the Eulerian finite strain versus normalized stress (f E–F E plot) leads to an almost horizontal trend, showing that a truncated second-order BM-EoS is appropriate to describe the elastic behavior of “Al5BO9” within the investigated P range. The weighted linear regression through the data points gives: F E(0) = 159(11) GPa. Axial compressibility coefficients yielded: β a  = 1.4(2) × 10?3 GPa?1, β b  = 3.4(4) × 10?3 GPa?1, and β c  = 1.7(3) × 10?3 GPa?1 (β a :β b :β c  = 1:2.43:1.21). The highest compressibilities observed in this study within (100) can be ascribed to the presence of voids represented by five-membered rings of polyhedra: Al1–Al3–Al4–Al1–Al3, which allow accommodating the effect of pressure by polyhedral tilting. Polyhedral tilting around the voids also explains the higher compressibility along [010] than along [001]. The stiffer crystallographic direction observed here might be controlled by the infinite chains of edge-sharing octahedra running along [100], which act as “pillars”, making the structure less compressible along the a-axis than along the b- and c-axis. Along [100], compression can only be accommodated by deformation of the edge-sharing octahedra (and/or by compression of the Al–O bond lengths), as no polyhedral tilting can occur. In addition, a comparative elastic analysis among the mullite-type materials is carried out.  相似文献   

3.
We experimentally investigated the phase relations of a peralkaline phonolitic dyke rock associated with the Ilímaussaq plutonic complex (South Greenland). The extremely evolved and iron-rich composition (magnesium number = 2, alkalinity index = 1.44, FeO* = 12 wt%) may represent the parental magma of the Ilímaussaq complex. This dyke rock is therefore perfectly suited for performing phase-equilibrium experiments, since in contrast to the plutonic rocks of the complex, no major cumulate formation processes complicate defining a reasonable starting composition. Experiments were carried out in hydrothermal rapid-quench cold-seal pressure vessels at P = 100 MPa and T = 950–750 °C. H2O contents ranging from anhydrous to H2O saturated (~5 wt% H2O) and varying fO2 (~ΔlogFMQ ?3 to +1; where FMQ represents the fayalite–magnetite–quartz oxygen buffer) were applied. Reduced and dry conditions lead to substantial crystallization of alkali feldspar, nepheline, hedenbergite-rich clinopyroxene, fayalite-rich olivine and minor amounts of ulvøspinel-rich magnetite, which represent the phenocryst assemblage of the natural dyke rock. Oxidized and H2O-rich conditions, however, suppress the crystallization of olivine in favor of magnetite and clinopyroxene with less or no alkali feldspar and nepheline formation. Accordingly, combined low fO2 and aH2O force the evolution of the residual melt toward decreasing SiO2, increasing FeO* and alkalinity index (up to 3.55). On the contrary, high fO2 and aH2O produce residual melts with relatively low FeO*, high SiO2 and a relatively constant alkalinity index. We show that variations of aH2O and fO2 lead to contrasting trends regarding the liquid lines of descent of iron-rich silica-undersaturated peralkaline compositions. Moreover, the increase in FeO* and alkalinity index (reduced and dry conditions) in the residual melt is an important prerequisite to stabilize late-magmatic minerals of the dyke rock, for example, aenigmatite (Na2Fe5TiSi6O20), coexisting with the most evolved melts at 750 °C. Contrary to what might be expected, experiments with high aH2O and interlinked high fO2 exhibit higher liquidus T’s compared with experiments performed at low aH2O and fO2 for experiments where magnetite is liquidus phase. This is because ulvøspinel-poor magnetite crystallizes at higher fO2 and has a higher melting point than ulvøspinel-rich magnetite, which is favored at lower fO2.  相似文献   

4.
The stress [crack damage stress (σ cd) and uniaxial compressive strength (σ c)] and strain characteristics [maximum total volumetric strain (ε cd), axial failure strain (ε af)], porosity (n) and elastic constants [elastic modulus (E) and Poisson’s ratio (ν)] and their ratios were coordinated with the existence of two different types (type 1 and type 2) of volumetric strain curve. Type 1 volumetric strain curve has a reversal point and, therefore, σ cd is less than the uniaxial compressive strength (σ c). Type 2 has no reversal point, and the bulk volume of rock decreases until its failure occurs (i.e., σ cd = σ c). It is confirmed that the ratio between the elastic modulus (E) and the parameter λ = n/ε cd strongly affects the crack damage stress (σ cd) for both type 1 and type 2 volumetric strain curves. It is revealed that heterogeneous carbonate rock samples exhibit different types of the volumetric strain curve even within the same rock formation, and the range of σ cd/σ c = 0.54–1 for carbonate rocks is wider than the range (0.71 < σ cd/σ c < 0.84) obtained by other researchers for granites, sandstones and quartzite. It is established that there is no connection between the type of the volumetric strain curve and values of n, E, σ cd, ν, E/(1 ? 2ν), M R = E/σ c and E/λ. On the other hand, the type of volumetric strain curve is connected with the values of λ and the ratio between the axial failure strain (ε af) and the maximum total volumetric strain (ε cd). It is argued that in case of small ε af/ε cd–small λ, volumetric strain curve follows the type 2.  相似文献   

5.
In situ X-ray diffraction measurements of KAlSi3O8-hollandite (K-hollandite) were performed at pressures of 15–27 GPa and temperatures of 300–1,800 K using a Kawai-type apparatus. Unit-cell volumes obtained at various pressure and temperature conditions in a series of measurements were fitted to the high-temperature Birch-Murnaghan equation of state and a complete set of thermoelastic parameters was obtained with an assumed K′300,0=4. The determined parameters are V 300,0=237.6(2) Å3, K 300,0=183(3) GPa, (?K T,0/?T) P =?0.033(2) GPa K?1, a 0=3.32(5)×10?5 K?1, and b 0=1.09(1)×10?8 K?2, where a 0 and b 0 are coefficients describing the zero-pressure thermal expansion: α T,0 = a 0 + b 0 T. We observed broadening and splitting of diffraction peaks of K-hollandite at pressures of 20–23 GPa and temperatures of 300–1,000 K. We attribute this to the phase transitions from hollandite to hollandite II that is an unquenchable high-pressure phase recently found. We determined the phase boundary to be P (GPa)=16.6 + 0.007 T (K). Using the equation of state parameters of K-hollandite determined in the present study, we calculated a density profile of a hypothetical continental crust (HCC), which consists only of K-hollandite, majorite garnet, and stishovite with 1:1:1 ratio in volume. Density of HCC is higher than the surrounding mantle by about 0.2 g cm?3 in the mantle transition zone while this relation is reversed below 660-km depth and HCC becomes less dense than the surrounding mantle by about 0.15 g cm?3 in the uppermost lower mantle. Thus the 660-km seismic discontinuity can be a barrier to prevent the transportation of subducted continental crust materials to the lower mantle and the subducted continental crust may reside at the bottom of the mantle transition zone.  相似文献   

6.
This study presents bulk chemical compositions of the Tongmuling soil profile, which developed on dolostone, and the overlying strata covering the bedrock in the central Guizhou province (southern China). The chemical weathering characteristics of the studied profile were investigated and the inheritance relationships between the terra rossa and overlying strata were discussed. The results show that there is no remarkable variation in the major elements and weathering indices from the rock–soil interface to the topsoil, indicating that the studied profile was not typical for in situ crustal chemical weathering. The terra rossa were mainly composed of SiO2, Al2O3 and Fe2O3. Compared with the insoluble residues and overlying strata, the terra rossa are characterized by an enrichment of Y and Cs and depletion of Ba and Sr. The subsoil shows a notable Ce negative anomaly, characterized by heavy rare earth element enrichment (L/H = 1.55–3.74), whereas the topsoil shows a positive Ce anomaly with light rare earth element enrichment (L/H = 5.93–9.14). According to Laterite-forming capacity estimates, the terra rossa could not have only been formed from acid-insoluble residues from the bedrock; Al2O3 versus Fe2O3 and Nb plotted against Ta show significant positive correlations between the terra rossa and overlying strata. The Eu/Eu* versus GdN/YbN and ternary diagrams for Sc, Th, Zr, and Ta suggest that the overlying strata could also provide parent materials for the genesis of terra rossa.  相似文献   

7.
The single-crystal elastic constants of natural alunite (ideally KAl3(SO4)2(OH)6) were determined by Brillouin spectroscopy. Chemical analysis by electron microprobe gave a formula KAl3(SO4)2(OH)6. Single crystal X-ray diffraction refinement with R 1 = 0.0299 for the unique observed reflections (|F o| > 4σ F) and wR 2 = 0.0698 for all data gave a = 6.9741(3) Å, c = 17.190(2) Å, fractional positions and thermal factors for all atoms. The elastic constants (in GPa), obtained by fitting the spectroscopic data, are C 11 = 181.9 ± 0.3, C 33 = 66.8 ± 0.8, C 44 = 42.8 ± 0.2, C 12 = 48.2 ± 0.5, C 13 = 27.1 ± 1.0, C 14 = 5.4 ± 0.5, and C 66 = ½(C 11–C 12) = 66.9 ± 0.3 GPa. The VRH averages of bulk and shear modulus are 63 and 49 GPa, respectively. The aggregate Poisson ratio is 0.19. The high value of the ratio C 11/C 33 = 2.7 and of the ratio C 66/C 44 = 1.6 are characteristic of an anisotropic structure with very weak interlayer interactions along the c-axis. The basal plane (001) is characterized by 0.1% longitudinal acoustic anisotropy and 0.9–1.1% shear acoustic anisotropy, which gives alunite a characteristic pseudo-hexagonal elastic behavior, and is related to the pseudo-hexagonal arrangement of the Al(O,OH)6 octahedra in the basal layer. The elastic Debye temperature of alunite is 654 K. The large discrepancy between the elastic and heat capacity Debye temperature is also a consequence of the layered structure.  相似文献   

8.
Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively.  相似文献   

9.
In this paper, a study on the performance of surface irrigation of date palms in a Tunisian arid area (Douz oasis) is presented. The study is conducted in 16 plots with various sizes and soil textures over a 4-year period (2012–2015). In the first step, an assessment of total water requirements of the date palms is carried out. Then, the surface irrigation performance is analyzed using three indicators, i.e., the relative water supply (RWS) indicator, the uniformity index of water distribution (D U ), and the water application efficiency (E a ). Finally, the irrigation management problems are identified. The results indicate that in the arid Tunisian Saharan oases, the soil texture, plot size, and farmers’ practices (especially irrigation duration) have significant effects on surface irrigation performance. The average annual net irrigation requirements of date palms are about 2400 mm. The RWS increases from 1.8 in the smaller plots (0.5 ha) to 3.6 in the largest plots (2.5 ha), implying that the increase in the plot size requires an excessive water supply. D U decreases from 80.7 in the 0.5 ha plots to 65.4 in the 2.5 ha plots; however, no significant difference in the E a is observed. The results show that the soil texture has no influence on the RWS and D U , but the E a is significantly higher in the loamy-sand soils (46.7%) compared to the sandy soils (36.3%). Overall, RWS indicator is higher than 1 (RWS?=?2.6) implying excessive irrigation supply to the system. Although D U is relatively uniform (>?60%), E a is relatively low (<?50%) indicating that the current irrigation management is inefficient. These findings have a paramount importance for improving irrigation water management in the Tunisian Saharan oases.  相似文献   

10.
Sized aggregates of glasses (47–84 wt% SiO2) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their 39Ar diffusion properties (average E=33,400 cal mol?1; D o=4.63×10?3 cm2 s?1). At T<~1,000 °C, glasses containing <~69 wt% SiO2 and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log10 unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield 40Ar/39Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.  相似文献   

11.
The crystal chemistry across the garnet series is examined, and several systematic trends are reported. The crystal structure of three different cubic phases intergrown in a birefringent near end-member andradite from Namibia was refined by the Rietveld method, space group $ Ia\bar{3}d, $ Ia 3 ¯ d , and monochromatic synchrotron high-resolution powder X-ray diffraction data. Electron microprobe results indicate three phases with distinct compositions. The sample is birefringent, indicating that it is not cubic when observed optically. The reduced χ 2 and overall R (F 2) Rietveld refinement values are 1.655 and 0.0284, respectively, so the multi-phase refinement is excellent. The composition, weight %, unit-cell parameter (Å), distances (Å), and site-occupancy factors (sofs) are as follows: phase-1, Adr99, 88.5(1)  %, a = 12.06259(1), average 〈Ca–O〉 = 2.4310, Fe–O = 2.0189(4), Si–O = 1.6490(4) Å, Ca(sof) = 0.948(1), Fe(sof) = 0.934(1), and Si(sof) = 0.940(1). For phase-2: Adr71Grs28, 7.1(1) %, a = 12.00361(5), average 〈Ca–O〉 = 2.440, Fe–O = 1.979(3), Si–O = 1.641(3) Å, Ca(sof) = 0.913(5), Fe(sof) = 0.767(4), and Si(sof) = 0.932(5). For phase-3: Grs79Adr17, 4.4(1) %, a = 11.89719(4), average 〈Ca–O〉 = 2.404, Al–O = 1.935(4), Si–O = 1.667(3) Å, Ca(sof) = 0.944(6), Al(sof) = 1.069(7), and Si(sof) = 0.887(5). The dominant phase-1 (89 %; Adr99) is nearly end-member andradite, Ca3Fe 2 3+ Si3O12, which contains no cation order in the Ca(X) or Fe(Y) sites. The intergrowth of the three cubic phases causes considerable strain in the minor phases-2 and phases-3 that arise from different structural parameters and gives rise to strain-induced birefringence. For comparison, the results for an isotropic, single-phase, grossular–andradite garnet (Grs76Adr21) are also presented. The strain in the minor phases is about 3–5 times more than the unstrained dominant phase-1, or the unstrained single-phase grossular–andradite.  相似文献   

12.
Wadeite-type K2Si4O9 was synthesized with a cubic press at 5.4 GPa and 900 °C for 3 h. Its unit-cell parameters were measured by in situ high-T powder X-ray diffraction up to 600 °C at ambient P. The T–V data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (αT = a 0 + a 1 T), yielding a 0 = 2.47(21) × 10?5 K?1 and a 1 = 1.45(36) × 10?8 K?2. Compression experiments at ambient T were conducted up to 10.40 GPa with a diamond-anvil cell combined with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the P–V data, yielding K T = 97(3) GPa and V 0 = 360.55(9) Å3. These newly determined thermal expansion data and compression data were used to thermodynamically calculate the P–T curves of the following reactions: 2 sanidine (KAlSi3O8) = wadeite (K2Si4O9) + kyanite (Al2SiO5) + coesite (SiO2) and wadeite (K2Si4O9) + kyanite (Al2SiO5) + coesite/stishovite (SiO2) = 2 hollandite (KAlSi3O8). The calculated phase boundaries are generally consistent with previous experimental determinations.  相似文献   

13.
A new pyroxene with formula (Na0.86Mg0.14)(Mg0.57Ti0.43)Si2O6, synthesized in a high-pressure toroidal ‘anvil-with-hole’ apparatus at P = 7 GPa and T = 1700 °C, was characterized by X-ray single-crystal diffraction and Raman spectroscopy. The compound was found to be monoclinic (R1 = 2.56 %), space group C2/c, with lattice parameters a = 9.687(2), b = 8.814(1), c = 5.290(1) Å, β = 107.853(2)°, V = 430.08(1) Å3. The coexistence of Mg and Ti4+ at the M1 site does not induce strong modifications either to the M1 site or to the adjacent M2 site. The Raman spectrum of synthetic Na–Ti-pyroxene was obtained for the first time and compared with that of Mg2Si2O6 (with very low concentrations of Na and Ti). The structural characterization of the Na–Ti–Mg-pyroxene is important, because the study of its thermodynamic constants provides new constraints on thermobarometry of the upper mantle assemblages.  相似文献   

14.
The behavior of a natural topaz, Al2.00Si1.05O4.00(OH0.26F1.75), has been investigated by means of in situ single-crystal synchrotron X-ray diffraction up to 45 GPa. No phase transition or change in the compressional regime has been observed within the pressure-range investigated. The compressional behavior was described with a third-order Birch–Murnaghan equation of state (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are as follows: K V = 158(4) GPa and K V ′ = 3.3(3). The confidence ellipse at 68.3 % (Δχ2 = 2.30, 1σ) was calculated starting from the variance–covariance matrix of K V and K′ obtained from the III-BM-EoS least-square procedure. The ellipse is elongated with a negative slope, indicating a negative correlation of the parameters K V and K V ′, with K V = 158 ± 6 GPa and K V ′ = 3.3 ± 4. A linearized III-BM-EoS was used to obtain the axial-EoS parameters (at room-P), yielding: K(a) = 146(5) GPa [β a = 1/(3K(a)) = 0.00228(6) GPa?1] and K′(a) = 4.6(3) for the a-axis; K(b) = 220(4) GPa [β b = 0.00152(4) GPa?1] and K′(b) = 2.6(3) for the b-axis; K(c) = 132(4) GPa [β c = 0.00252(7) GPa?1] and K′(c) = 3.3(3) for the c-axis. The elastic anisotropy of topaz at room-P can be expressed as: K(a):K(b):K(c) = 1.10:1.67:1.00 (β a:β b:β c = 1.50:1.00:1.66). A series of structure refinements have been performed based on the intensity data collected at high pressure, showing that the P-induced structure evolution at the atomic scale is mainly represented by polyhedral compression along with inter-polyhedral tilting. A comparative analysis of the elastic behavior and P/T-stability of topaz polymorphs and “phase egg” (i.e., AlSiO3OH) is carried out.  相似文献   

15.
MgSiO3 akimotoite is stable relative to majorite-garnet under low-temperature geotherms within steeply or rapidly subducting slabs. Two compositions of Mg–akimotoite were synthesized under similar conditions: Z674 (containing about 550 ppm wt H2O) was synthesized at 22 GPa and 1,500 °C and SH1101 (nominally anhydrous) was synthesized at 22 GPa and 1,250 °C. Crystal structures of both samples differ significantly from previous studies to give slightly smaller Si sites and larger Mg sites. The bulk thermal expansion coefficients of Z674 are (153–839 K) of a 1 = 20(3) × 10?9 K?2 and a 0 = 17(2) × 10?6 K?1, with an average of α 0 = 27.1(6) × 10?6 K?1. Compressibility at ambient temperature of Z674 was measured up to 34.6 GPa at Sector 13 (GSECARS) at Advanced Photon Source Argonne National Laboratory. The second-order Birch–Murnaghan equation of state (BM2 EoS) fitting yields: V 0 = 263.7(2) Å3, K T0 = 217(3) GPa (K′ fixed at 4). The anisotropies of axial thermal expansivities and compressibilities are similar: α a  = 8.2(3) and α c  = 10.68(9) (10?6 K?1); β a  = 11.4(3) and β c  = 15.9(3) (10?4 GPa). Hydration increases both the bulk thermal expansivity and compressibility, but decreases the anisotropy of structural expansion and compression. Complementary Raman and Fourier transform infrared (FTIR) spectroscopy shows multiple structural hydration sites. Low-temperature and high-pressure FTIR spectroscopy (15–300 K and 0–28 GPa) confirms that the multiple sites are structurally unique, with zero-pressure intrinsic anharmonic mode parameters between ?1.02 × 10?5 and +1.7 × 10?5 K?1, indicating both weak hydrogen bonds (O–H···O) and strong OH bonding due to long O···O distances.  相似文献   

16.
The time scales and mechanics of gravitationally driven crystal settling and compaction is investigated through high temperature (1,280–1,500 °C) centrifuge-assisted experiments on a chromite-basalt melt system at 100–1,500g (0.5 GPa). Subsequently, the feasibility of this process for the formation of dense chromite cumulate layers in large layered mafic intrusions (LMIs) is assessed. Centrifugation leads to a single cumulate layer formed at the gravitational bottom of the capsule. The experimentally observed mechanical settling velocity of a suspension of ~24 vol% chromite is calculated to be about half (~0.53) of the Stokes settling velocity, with a sedimentation exponent n of 2.35 (3). Gravitational settling leads to an orthocumulate layer with a porosity of 0.52 (all porosities as fraction). Formation times for such a layer from a magma with initial chromite contents of 0.1–1 vol% are 140–3.5 days, equal to a growth rate of 0.007–0.3 m/day for grain sizes of 1–2 mm. More compacted chromite layers form with increasing centrifugation time and acceleration through chemical compaction: An increase of grain contact areas and grain sizes together with a decrease in porosity is best explained by pressure dissolution at grain contacts, reprecipitation and grain growth into the intergranular space and a concomitant expulsion of intergranular melt. The relation between the porosity in the cumulate pile and effective pressure integrated over time (Δρ · h · a · t) is best fit with a logarithmic function, in fact confirming that a (pressure) dissolution–reprecipitation process is the dominant mechanism of compaction. The experimentally derived equation allows calculating compaction times: 70–80 % chromite at the bottom of a 1-m-thick chromite layer are reached after 9–250 years, whereas equivalent compaction times are 0.2–0.9 years for olivine (both for 2 mm grain size). The experiments allow to determine the bulk viscosities of chromite and olivine cumulates to be of magnitude 109 Pa s, much lower than previously reported. As long as melt escape from the compacting cumulate remains homogeneous, fluidization does not play any role; however, channelized melt flow may lead to suspension and upward movement of cumulate crystals. In LMIs, chromitite layers are typically part of a sequence with layers of mafic minerals, compaction occurs under the additional weight of the overlying layers and can be achieved in a few years to decades.  相似文献   

17.
Heavy metals are governed by parent material of soils and influenced by the soil physicochemical properties and soil and crop management practices. This paper evaluates total heavy metal concentrations in rainfed soils under diverse management practices of tropical India. Vertisols (clayey soils with high shrink/swell capacity) had the highest concentrations of heavy metals. However, chromium (Cr) content was above the threshold value in Aridisol [calcium carbonate (CaCO3)]-containing soils of the arid environments with subsurface horizon development. Concentration increased at lower depths (>30 cm). Basaltic soils showed higher concentrations of nickel (Ni), copper (Cu) and manganese (Mn). Cadmium (Cd), cobalt (Co), Cu and Mn concentrations were higher in soils cultivated to cotton, whereas Cr concentration was above the threshold level of 110 mg kg?1 in food crop cultivated soils. As the specific soil surface is closely related to clay content and clay type, soil’s ability to retain heavy metals is more closely tied to the specific surface than to the soil cation exchange capacity. Higher positive correlations were found between heavy metal concentrations and clay content [Cd(r = 0.85; p ≤ 0.01); Co (r = 0.88; p ≤ 0.05); Ni (r = 0.87; p ≤ 0.01); Co (r = 0.81; p ≤ 0.05); Zn (r = 0.49; p ≤ 0.01); Cr (r = 0.80; p ≤ 0.05); Mn (r = 0.79; p ≤ 0.01)]. The amounts of nitrogen–phosphorus–potassium applied showed a positive correlation with Co and Ni (r = 0.62; p ≤ 0.05). As several soils used for growing food crops are high in Ni, Cr and Mn, the flow of these metals in soil–plant–livestock/human chain needs further attention.  相似文献   

18.
Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K 0 = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α 0 = 4.39 (27) × 10?5 K?1 and temperature derivative of the bulk modulus (?K/?T) P  = ?0.009 (6) GPa K?1 were obtained. The axial thermoelastic properties were also obtained with K a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α a0 = 1.00 (11) × 10?5 K?1 for the a-axis, and K c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α c0 = 2.41 (24) × 10?5 K?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.  相似文献   

19.
《Applied Geochemistry》1998,13(6):779-785
The base mediated and neutral abiotic reactions of 4 chlorinated aliphatic compounds have been studied as a function of temperature and pH. Arrhenius parameters obtained for base mediated reactions were as follows: 1,1,2-trichloroethane, log10A=14.36±0.55, Ea=95.6±3.6 kJ/mol; 1,1,1,2-tetrachloroethane, log10A=14.56±0.33, Ea=101.4±2.1 kJ/mol; 1,2,3-trichloropropane, log10A=13.31±0.53, Ea=95.9±3.5 kJ/mol. For the neutral reaction of 2,3-dichloro-1-propene the Arrhenius parameters were log10A=10.2±1.3, Ea=98±9 kJ/mol. For 1,1,2-trichloroethane the product of the base mediated reaction was identified as 1,1-dichloroethene, in contrast to previous studies. 2,3-dichloro-1-propene was found as an intermediate in the base mediated reaction of 1,2,3-trichloropropane, with 2-chloro-2-propen-1-ol as the major final product. Results from the present study are compared to those found in previous work.  相似文献   

20.
In-situ Rock Spalling Strength near Excavation Boundaries   总被引：2，自引：0，他引：2  
It is widely accepted that the in-situ strength of massive rocks is approximately 0.4 ± 0.1 UCS, where UCS is the uniaxial compressive strength obtained from unconfined tests using diamond drilling core samples with a diameter around 50 mm. In addition, it has been suggested that the in-situ rock spalling strength, i.e., the strength of the wall of an excavation when spalling initiates, can be set to the crack initiation stress determined from laboratory tests or field microseismic monitoring. These findings were supported by back-analysis of case histories where failure had been carefully documented, using either Kirsch’s solution (with approximated circular tunnel geometry and hence σ max = 3σ 1 ?σ 3) or simplified numerical stress modeling (with a smooth tunnel wall boundary) to approximate the maximum tangential stress σ max at the excavation boundary. The ratio of σ max /UCS is related to the observed depth of failure and failure initiation occurs when σ max is roughly equal to 0.4 ± 0.1 UCS. In this article, it is suggested that these approaches ignore one of the most important factors, the irregularity of the excavation boundary, when interpreting the in-situ rock strength. It is demonstrated that the “actual” in-situ spalling strength of massive rocks is not equal to 0.4 ± 0.1 UCS, but can be as high as 0.8 ± 0.05 UCS when surface irregularities are considered. It is demonstrated using the Mine-by tunnel notch breakout example that when the realistic “as-built” excavation boundary condition is honored, the “actual” in-situ rock strength, given by 0.8 UCS, can be applied to simulate progressive brittle rock failure process satisfactorily. The interpreted, reduced in-situ rock strength of 0.4 ± 0.1 UCS without considering geometry irregularity is therefore only an “apparent” rock strength.  相似文献   

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