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1.
Experiments reproducing the development of bimetasomatic zoning in the CaO-MgO-SiO2-H2O-CO2 system were conducted at elevated P-T parameters with the use of samples of naturally occurring quartzdolomite and calcite-serpentinite rocks. In order to maintain mass transfer exclusively via the diffusion-controlled mechanism, we used the method of the ensured compaction of the cylindrical sample surface with a thin-walled gold tube. In the course of the experiments, a single diopside zone ～2.5 × 10?5 m thick was obtained at the quartz-dolomite interface at T = 600°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.5 for 25–40 days and a succession of metasomatic zones at T = 750°C, $P_{H_2 O + CO_2 } $ = 300 MPa, and $X_{CO_2 } $ = 0.4 for 48 days. The metasomatic zones were as follows (listed in order from quartz to dolomite): wollastonite ‖ diopside ‖ tremolite ‖ calcite + forsterite; with the average width of the diopside zone equal to ～1.3 × 10?5 m and the analogous part of the wollastonite zone equal to ～2.6 × 10?5 m. Two zones (listed in order from calcite to serpentine) diopside and diopside-forsterite (the average widths of these zones were ～6 × 10?4 and ～8 × 10?4 m, respectively) were determined to develop at contact between serpentine and calcite during experiments that lasted 124 days at T = 500°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.2–0.4. In the former and latter situations, the growth rate of the zoning ranged between 3.1 × 10?12 and 1.2 × 10?11 m/s and between 5.6 × 10?11 and 7.5 × 10?11 m/s, respectively. The higher growth rate in the latter case can be explained by the higher water mole fraction in the fluid, with this water released during serpentinite decomposition in the experiments. The development of the only diopside zone in the experiments modeling the interaction of quartz and dolomite at T = 600–650°C and $P_{H_2 O + CO_2 } $ = 200 MPa is in conflict with theoretical considerations underlain by the Korzhinskii-Fisher-Joesten model. The interaction of quartz and dolomite in the CaO-MgO-SiO2-CO2-H2O system at the P-T- $X_{CO_2 } $ parameters specified above should be attended by the origin of a number of reaction zones consisting of various proportions of talc, forsterite, tremolite, diopside, and calcite. The saturation of the fluid with respect to these minerals was likely not reached, and this resulted in the degeneration of the respective stability fields in the succession of zones. Conceivably, this was related to the insufficient rates of quartz and dolomite dissolution and the relatively low diffusion rates of the dissolved species in the low-permeable medium. In the experiments with interacting calcite and serpentine, the zoning calcite ‖ diopside ‖ diopside + forsterite ‖ serpentine developed in its complete form, in agreement with the theory. Equilibrium was likely achieved in these experiments due to the higher diffusion coefficients.  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.
The crystal structure of four birefringent andradite samples (two from Arizona, one from Madagascar, and one from Iran) was refined with the Rietveld method, space group $Ia\overline{3} d$ , and monochromatic synchrotron high-resolution powder X-ray diffraction (HRPXRD) data. Each sample contains an assemblage of three different cubic phases. From the electron-microprobe (EMPA) results, fine-scale intergrowths in the Arizona-2 and Madagascar samples appear homogeneous with nearly identical compositions of {Ca2.99Mg0.01}Σ3[ ${\text{Fe}}_{1.99}^{3 + }$ ${\text{Mn}}_{0.01}^{3 + }$ ]Σ2(Si2.95Al0.03 ${\text{Fe}}_{0.02}^{3 + }$ )Σ3O12, Adr98 (Arizona-2), and Adr97 (Madagascar). Both samples are near-end-member andradite, ideally {Ca3}[ ${\text{Fe}}_{2}^{3 + }$ ](Si3)O12, so cation ordering in the X, Y, or Z sites is not possible. Because of the large-scale intergrowths, the Arizona-1 and Iran samples contain three different compositions. Arizona-1 has compositions Adr97 (phase-1), Adr93Grs4 (phase-2), and Adr87Grs11 (phase-3). Iran sample has compositions Adr86Uv12 (phase-1), Adr69Uv30 (phase-2), and Adr76Uv22 (phase-3). The crystal structure of the three phases within each sample was modeled quite well as indicated by the Rietveld refinement statistics of reduced χ2 and overall R (F 2) values of, respectively, 1.980 and 0.0291 (Arizona-1); 1.091 and 0.0305 (Arizona-2); 1.362 and 0.0231 (Madagascar); and 1.681 and 0.0304 (Iran). The dominant phase for each sample has the following unit-cell parameters (Å) and weight fractions (%): a = 12.06314(1), 51.93(9) (Arizona-1); 12.04889(1), 52.47(1) (Arizona-2); 12.06276(1), 52.21(8) (Madagascar); and 12.05962(2), 63.3(1) (Iran). For these dominant phases, the distances and site occupancy factors (sofs) in terms of neutral atoms at the Ca(X), Fe(Y), and Si(Z) sites are as follows: <Ca–O> = 2.4348, Fe–O = 2.0121(6), Si–O = 1.6508(6) Å; Ca(sof) = 0.955(2), Fe(sof) = 0.930(2), and Si(sof) = 0.917(2) (Arizona-1); <Ca–O> = 2.4288, Fe–O = 2.0148(7), Si–O = 1.6476(7) Å; Ca(sof) = 0.953(2), Fe(sof) = 0.891(2), and Si(sof) = 0.927(2) (Arizona-2); <Ca–O> = 2.4319, Fe–O = 2.0220(6), Si–O = 1.6460(6) Å; Ca(sof) = 0.955(2), Fe(sof) = 0.941(2), and Si(sof) = 0.939(2) (Madagascar); and <Ca–O> = 2.4344, Fe–O = 2.0156(8), Si–O = 1.6468(8) Å; Ca(sof) = 0.928(2), Fe(sof) = 0.908(2), and Si(sof) = 0.932(3) (Iran). The sofs based on the EMPA results are similar to those obtained from the Rietveld refinement. Each phase in the HRPXRD results can be correlated with a specific chemical composition. For example, the Iran sample composition Adr63Uv30 corresponds to phase-3 that has the smallest unit-cell parameter; Adr76Uv22 corresponds to phase-1 that has the intermediate cell value; and Adr86Uv13 corresponds to phase-2 that has the largest unit-cell parameter. The bond distances compare well with those obtained from radii sum. The three different cubic phases in each sample cause strain that arises from the mismatch of the cubic unit-cell parameters and give rise to birefringence.  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.
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   

6.
This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition IV(Si2.76Al1.24) VI(Al0.64Mg0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn0.03Ti0.15) (K0.96Na0.05) O10.67 (OH)1.31 Cl0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition IV(Si3.14Al0.86)VI(Al0.75Mg0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn0.01Ti0.01Li1.09) (K0.99Na0.01) O10.00 (OH)0.65F1.35]. Samples differ for Fe ordering in octahedral sites, Fe2+/(Fe2+?+?Fe3+) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.  相似文献   

7.
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   

8.
In the present work we studied Mg-ilmenite megacrysts from the Arkhangelsk kimberlites (the Kepino kimberlite field and mantle xenoliths from the Grib pipe). On the basis of isotopic (Rb/Sr, Sm/Nd, δ18O) and trace-element data we argue that studied Mg-ilmenite megacrysts have a genetic relation to the “protokimberlitic” magma, which was parental to the host kimberlites. Rb-Sr ages measured on phlogopite from ilmenite-clinopyroxenite xenoliths and the host Grib kimberlite overlap within the error (384 Ma and 372 ± 8 Ma, respectively; Shevchenko et al., 2004) with our estimation of the Kotuga kimberlite emplacement (378 ± 25 Ma). Sr and Nd isotopic compositions of megacrysts are close to the isotopic composition of host kimberlites (Mg-ilmenites from kimberlites have 87Sr/86Sr(t = 384) = 0.7050–0.7063, ?Nd(t = 384) = + 1.7, +1.8, ilmenite from ilmenite-garnet clinopyroxenite xenolith has 87Sr/86St(t = 384) = 0.7049, ?Nd(t = 384) = +3.5). Oxygen isotopic composition of ilmenites (δ18O = +3.8–+4.5‰) is relatively “light” in comparison with the values for mantle minerals (δ18O = +5–+6‰). Taking into account ilmenite-melt isotope fractionation, these values of δ18O indicate that ilmenites could crystallize from the “protokimberlitic” melt. Temperatures and redox conditions during the formation of ilmenite reaction rims were estimated using ilmenite-rutile and titanomagnetite-ilmenite thermo-oxybarometers. New minerals within the rims crystallized at increasing oxygen fugacity and decreasing temperature. Spinels precipitated during the interaction of ilmenite with kimberlitic melt at T = 1000–1100°C and oxygen fugacity $\Delta \log f_{O_2 }$ [QFM] ≈ 1. Rims comprised with rutile and titanomagnetite crystallized at T ≈ 1100°C, $\Delta \log f_{O_2 }$ [NNO] ≈ 4 and T = 600–613°C, $\Delta \log f_{O_2 }$ [QFM] ≈ 3.7, respectively. Rutile lamellae within ilmenite grains from clinopyroxenitic xenolith were formed T ≥ 1000–1100°C and oxygen fugacity $\Delta \log f_{O_2 }$ [NNO] = ?3.7. Since the pressure of clinopyroxene formation from this xenolith was estimated to be 45–53 kbar, redox conditions at 135–212 km depths could be close to $\Delta \log f_{O_2 }$ [NNO] = ?3.7.  相似文献   

9.
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   

10.
The partitioning of Fe and Mg between garnet and aluminous orthopyroxene has been experimentally investigated in the pressure-temperature range 5–30 kbar and 800–1,200° C in the FeO-MgO-Al2O3-SiO2 (FMAS) and CaO-FeO-MgO-Al2O3-SiO2 (CFMAS) systems. Within the errors of the experimental data, orthopyroxene can be regarded as macroscopically ideal. The effects of Calcium on Fe-Mg partitioning between garnet and orthopyroxene can be attributed to non-ideal Ca-Mg interactions in the garnet, described by the interaction term:W CaMg ga -W CaFe ga =1,400±500 cal/mol site. Reduction of the experimental data, combined with molar volume data for the end-member phases, permits the calibration of a geothermometer which is applicable to garnet peridotites and granulites: $$T(^\circ C) = \left\{ {\frac{{3,740 + 1,400X_{gr}^{ga} + 22.86P(kb)}}{{R\ln K_D + 1.96}}} \right\} - 273$$ with $$K_D = {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } \mathord{\left/ {\vphantom {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}} \right. \kern-\nulldelimiterspace} {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}$$ and $$X_{gr}^{ga} = (Ca/Ca + Mg + Fe)^{ga} .$$ The accuracy and precision of this geothermometer are limited by largerelative errors in the experimental and natural-rock data and by the modest absolute variation inK D with temperature. Nevertheless, the geothermometer is shown to yield reasonable temperature estimates for a variety of natural samples.  相似文献   

11.
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   

12.
Paragneisses of the Ivrea-Verbano zone exhibit over a horizontal distance of 5 km mineralogical changes indicative of the transition from amphibolite to granulite facies metamorphism. The most obvious change is the progressive replacement of biotite by garnet via the reaction: a $${\text{Biotite + sillimanite + quartz }} \to {\text{ Garnet + K - feldspar + H}}_{\text{2}} {\text{O}}$$ which results in a systematic increase in the modal ratio g = (garnet)/(garnet + biotite) with increasing grade. The systematic variations in garnet and biotite contents of metapelites are also reflected by the compositions of these phases, both of which become more magnesian with increasing metamorphic grade. The pressure of metamorphism has been estimated from the Ca3Al2Si3O12 contents of garnets coexisting with plagioclase, sillimanite and quartz. These phases are related by the equilibrium: b $$\begin{gathered} 3 CaAl_2 {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftharpoons Ca_3 Al_2 {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} + 2 Al_2 {\text{SiO}}_{\text{5}} + {\text{SiO}}_{\text{2}} \hfill \\ plagioclase garnet sillimanite quartz \hfill \\ \end{gathered} $$ which has been applied to these rocks using the available data on the mixing properties of plagioclase and garnet solid solutions. Temperature and f H 2O estimates have been made in a similar way using thermodynamic data on the biotite-garnet reaction (a) and the approximate solidus temperatures of paragneisses. Amphibolite to granulite facies metamorphism in the Ivrea-Verbano zone took place in the P-T ranges 9–11 kb and 700–820 °C. The differences in temperature and pressure of metamorphism between g= 0 and g = 1 (5 kms horizontal distance) were less than 50° C and approximately 1 kb. Retrogression and re-equilibration of garnets and biotites in the metapelites extended to temperatures more than 50° C below and pressures more than 1.5 kb below the peak of metamorphism, the degree of retrogression increasing with decreasing grade of the metamorphic “peak”. The pressure and temperature of the peak of metamorphism are not inconsistent with the hypothesis that the Ivrea-Verbano zone is a slice of upthrusted lower crust from the crust-mantle transition region, although it appears that the thermal gradient was too low for the zone to represent a near-vertical section through the crust. The most reasonable explanation of the granulite facies metamorphism is that it arose through intrusion of mafic rocks into a region already undergoing recrystallisation under amphibolite facies conditions.  相似文献   

13.
The chemistry of soil solutions can be altered by human activities, due to the intense agricultural and husbandry, leading to leaching of nutrients and subsequently elevating ground water levels. Multivariate statistical and inverse geochemical modeling techniques were used to determine the main factors controlling soil solution chemistry of calcareous soils. In this research, a total of 21 calcareous soils was characterized and assessed for soil solution using soil column. The major cations in the studied soil solutions were in the decreasing order as Ca2+ > Mg2+ > Na+ > K+. The anions were also arranged in decreasing order as HCO $ _{3}^{ - } $  > Cl $ ^{ - } $  > SO $ _{4}^{2 - } $  > NO $ _{3}^{ - } $ . Concentrations of NO $ _{3}^{ - } $ , P, and K+ in soil solutions were in the range of 6.8–307.5 mg l?1 (mean 63.2 mg l?1), 5.0–10.4 mg l?1 (mean 5.9 mg l?1), and 2.8–54.6 mg l?1 (mean 11.3 mg l?1), respectively. Results suggest that the concentration of P in the soil solutions could be primarily controlled by the solubility of dicalcium phosphate dihydrate and dicalcium phosphate. Interactions between soil properties and observed solubility of nutrients were described, and put into empirical multivariate formulations. Obtained equations contained electrical conductivity (EC) as a key factor in determining nutrients solubility. Inverse geochemical modeling of soil solution using PHREEQC indicates the dissolution of calcite, anhydrite, halite, CO2 (g), N2 (g), and hydroxyapatite, and precipitation of sulfur. Cation exchange between Ca2+, Mg2+, K+ and Na+ occurred with Mg2+ and K+ into the solution, and Ca2+ and Na+ out of the solution. Determination of soil solution will improve soil management in the area, and preventing groundwater deterioration.  相似文献   

14.
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   

15.
Piemontite- and thulite-bearing assemblages from highly oxidized metapelitic and metacalcareous schists associated with braunite quartzites at Vitali, Andros island, Greece, were chemically investigated. The Mn-rich metasediments are intercalated in a series of metapelitic quartzose schists, marbles, and basic metavolcanites which were affected by a regional metamorphism of the highP/T type (T=400–500° C,P>9 kb) and a later Barrovian-type greenschist metamorphism (T=400–500° C,P～-5–6 kb). Texturally and chemically two generations of piemontite (I and II) can be distinguished which may show complex compositional zoning. Piemontite I coexisted at highP/T conditions with braunite, manganian phengite (alurgite), Mn3+-Mn2+-bearing Na-pyroxene (violan), carbonate, quartz, hollandite, and hematite. Zoned grains generally exhibit a decreasing Mn3+ and an increasing Fe3+ and Al content towards the rim. Chemical compositions of piemontite I range from 2.0 to 32.1 mole % Mn3+, 0 to 25.6 mole % Fe3+, and 60.2 to 81.2 mole % Al. Up to 12.5 mole % Ca on the A(2) site can be substituted by Sr. Piemontites formed in contact or close to braunite (±hematite) attained maximum (Mn3++Fe3+)Al?1 substitution corrresponding to about 33 mole % Mn3++Fe3+ in lowiron compositions and up to about 39 mole % Mn3++ Fe3+ at intermediate Fe3+/(Fe3++Mn3+) ratios. Piemontite II which discontinuously overgrows piemontite I or occurs as separate grains may have been formed by greenschist facies decomposition of manganian Na-pyroxenes according to the reaction: (1) $$\begin{gathered} {\text{Mn}}^{{\text{3 + }}} - Mn^{2 + } - bearing omphacite/chloromelanite \hfill \\ + CO_2 + H_2 O + HCl \pm hermatite \hfill \\ = piemontite + tremolite + albite + chlorite \hfill \\ + calcite + quartz + NaCl \pm O_2 . \hfill \\ \end{gathered} $$ Thulites crystallized in coexistence with Al-rich piemontite II. All thulites analysed are low-Fe3+ manganian orthozoisites with Mntot～-Mn3+ substituting for Al on the M(3) site. Their compositions range from 2.9 to 7.2 mole % Mn3+, 0 to 1.2 mole % Fe3+, and 91.8 to 96.7 mole % Al. Piemontites II in thulite-bearing assemblages range from 5.8 to 15.9 mole % Mn3+, 0 to 3.7 mole % Fe3+, and 83.7 to 93.6 mole % Al. By contrast, piemontites II in thulite-free assemblages are similarly enriched in Mn3+ + Fe3+ — and partially in Sr2+ — as core compositions of piemontite I (21.1 to 29.6 mole % Mn3+, 2.0 to 16.5 mole % Fe3+, 60.6 to 68.4 mole % Al, 0 to 29.4 mole % Sr in the A(2) site). The analytical data presented in this paper document for the first time a continuous low-Fe3+ piemontite solid solution series from 5.8 to 32.1 mole % Mn3+. Aluminous piemontite II is enriched by about 3 mole % Mn3++Fe3+ relative to coexisting thulite in Fe3+-poor samples and by about 6 mole % Mn3++Fe3+ in more Fe3+-rich samples. Mineral pairs from different samples form a continuous compositional loop. Compositional shift of mineral pairs is attributed to the effect of a variable fluid composition at constantP fluid andT on the continuous reaction: (2) $$\begin{gathered} piemontite + CO_2 \hfill \\ = thulite + calcite + quartz \hfill \\ + Mn^{2 + } Ca_{ - 1} [calcite] + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ Further evidence for a variable \(x_{H_2 O} \) and/or \(f_{O_2 } \) possibly resulting from fluid infiltration and local buffering during the greenschist metamorphism is derived from the local decomposition of piemontite, braunite, and rutile to form spessartine, calcite, titanite, and hematite by the reactions: (3) $$\begin{gathered} piemontite + braunite + CO_2 \hfill \\ = sperssartine + calcite + quartz \pm hermatite \hfill \\ + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ and more rarely: (4) $$\begin{gathered} piemontite + quartz + rutile + braunite \hfill \\ = spessartine + titanite + hematite + H{_2} O + O{_2} . \hfill \\ \end{gathered} $$   相似文献   

16.
The stability relations between cordierite and almandite in rocks, having a composition of CaO poor argillaceous rocks, were experimentally investigated. The starting material consisted of a mixture of chlorite, muscovite, and quartz. Systems with widely varying Fe2+/Fe2++Mg ratios were investigated by using two different chlorites, thuringite or ripidolite, in the starting mixture. Cordierite is formed according to the following reaction: $${\text{Chlorite + muscovite + quartz}} \rightleftharpoons {\text{cordierite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} + {\text{H}}_{\text{2}} {\text{O}}$$ . At low pressures this reaction characterizes the facies boundary between the albite-epidotehornfels facies and the hornblende-hornfels facies, at medium pressures the beginning of the cordierite-amphibolite facies. Experiments were carried out reversibly and gave the following equilibrium data: 505±10°C at 500 bars H2O pressure, 513±10°C at 1000 bars H2O pressure, 527±10°C at 2000 bars H2O pressure, and 557±10°C at 4000 bars H2O pressure. These equilibrium data are valid for the Fe-rich starting material, using thuringite as the chlorite, as well as for the Mg-rich starting mixture with ripidolite. At 6000 bars the equilibrium temperature for the Mg-rich mixture is 587±10°C. In the Fe-rich mixture almandite was formed instead of cordierite at 6000 bars. The following reaction was observed: $${\text{Thuringite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Experiments with the Fe-rich mixture, containing Fe2+/Fe2++Mg in the ratio 8∶10, yielded three stability fields in a P,T-diagram (Fig.1):
  1. Above 600°C/5.25 kb and 700°C/6.5 kb almandite+biotite+Al2SiO5 coexist stably, cordierite being unstable.
  2. The field, in which almandite, biotite and Al2SiO5 are stable together with cordierite, is restricted by two curves, passing through the following points:
    1. 625°C/5.5 kb and 700°C/6.5 kb,
    2. 625°C/5.5 kb and 700°C/4.0 kb.
  3. At conditions below curves 1 and 2b, cordierite, biotite, and Al2SiO5 are formed, but no garnet.
An appreciable MnO-content in the system lowers the pressures needed for the formation of almandite garnet, but the quantitative influence of the spessartite-component on the formation of almandite could not yet be determined. the Mg-rich system with Fe2+/Fe2++Mg=0.4 garnet did not form at pressures up to 7 kb in the temperature range investigated. Experiments at unspecified higher pressures (in a simple squeezer-type apparatus) yielded the reaction: $${\text{Ripidolite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Further experiments are needed to determine the equilibrium data. The occurence of garnet in metamorphic rocks is discussed in the light of the experimental results.  相似文献   

17.
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   

18.
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   

19.
The diffusion of water in natural obsidian and model dacitic melts (Ab90Di8Wo2, mol %) has been studied at water vapor pressure up to 170 MPa, temperatures of 1200°C, H2O contents in melts up to ～6 wt % using a high gas pressure apparatus equipped with a unique internal device. The experiments were carried out by a new low-gradient technique with application of diffusion hydration of a melt from fluid phase. The water solubility in the melts and its concentration along $C_{H_2 O} $ diffusion profiles were determined using IR microspectrometry by application of the modified Bouguer-Beer-Lambert equation. A structural-chemical model was proposed to calculate and predict the concentration dependence of molar absorption coefficients of the hydroxyl groups (OH?) and water molecules (H2O) in acid polymerized glasses (quenched melts) in the obsidian-dacite series. The water diffusion coefficients $D_{H_2 O} $ were obtained by the mathematical analysis of concentration profiles and the analytical solution of the second Fick diffusion law using the Boltzman-Matano method. It was shown experimentally that $D_{H_2 O} $ exponentially increases with a growth of water concentration in the obsidian and dacitic melts within the entire range of diffusion profiles. Based on the established quantitative correlation between $D_{H_2 O} $ and viscosity of such melts, a new method was developed to predict and calculate the concentration, temperature, and pressure dependences of $D_{H_2 O} $ in acid magmatic melts (obsidian, rhyolite, albite, granite, dacite) at crustal T, P parameters and water concentrations up to 6 wt %.  相似文献   

20.
The enthalpy of formation of andradite (Ca3Fe2Si3O12) has been estimated as-5,769.700 (±5) kJ/mol from a consideration of the calorimetric data on entropy (316.4 J/mol K) and of the experimental phaseequilibrium data on the reactions: 1 $$\begin{gathered} 9/2 CaFeSi_2 O_6 + O_2 = 3/2 Ca_3 Fe_2 Si_3 O_{12} + 1/2 Fe_3 O_4 + 9/2 SiO_2 (a) \hfill \\ Hedenbergite andradite magnetite quartz \hfill \\ \end{gathered} $$ 1 $$\begin{gathered} 4 CaFeSi_2 O_6 + 2 CaSiO_3 + O_2 = 2 Ca_3 Fe_2 Si_3 O_{12} + 4 SiO_2 (b) \hfill \\ Hedenbergite wollastonite andradite quartz \hfill \\ \end{gathered} $$ 1 $$\begin{gathered} 18 CaSiO_3 + 4 Fe_3 O_4 + O_2 = 6Ca_3 Fe_2 Si_3 O_{12} (c) \hfill \\ Wollastonite magnetite andradite \hfill \\ \end{gathered} $$ 1 $$\begin{gathered} Ca_3 Fe_2 Si_3 O_{12} = 3 CaSiO_3 + Fe_2 O_3 . (d) \hfill \\ Andradite pseudowollastonite hematite \hfill \\ \end{gathered} $$ and $$log f_{O_2 } = E + A + B/T + D(P - 1)/T + C log f_{O_2 } .$$ Oxygen-barometric scales are presented as follows: $$\begin{gathered} E = 12.51; D = 0.078; \hfill \\ A = 3 log X_{Ad} - 4.5 log X_{Hd} ; C = 0; \hfill \\ B = - 27,576 - 1,007(1 - X_{Ad} )^2 - 1,476(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite (Ad)-hedenbergite (Hd)-magnetite-quartz: $$\begin{gathered} E = 13.98; D = 0.0081; \hfill \\ A = 4 log(X_{Ad} / X_{Hd} ); C = 0; \hfill \\ B = - 29,161 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite-hedenbergite-wollastonite-quartz: 1 $$\begin{gathered} E = 13.98;{\text{ }}D = 0.0081; \hfill \\ A = 4\log (X_{Ad} /X_{Hd} );{\text{ C = 0;}} \hfill \\ B = - 29,161 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite-hedenbergite-calcitequartz: 1 $$\begin{gathered} E = - 1.69;{\text{ }}D = - 0.199; \hfill \\ A = 4\log (X_{Ad} /X_{Hd} );{\text{ C = 2;}} \hfill \\ B = - 20,441 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 . \hfill \\ \end{gathered} $$ For the assemblage andradite-hedenbergite-wollastonite-calcite: 1 $$\begin{gathered} E = - 17.36;{\text{ }}D = - 0.403; \hfill \\ A = 4\log (X_{Ad} /X_{Hd} );{\text{ C = 4;}} \hfill \\ B = - 11,720 - 1,342.8(1 - X_{Ad} )^2 - 1,312(1 - X_{Hd} )^2 \hfill \\ \end{gathered} $$ The oxygen fugacity of formation of those skarns where andradite and hedenbergite assemblage is typical can be calculated by using the above equations. The oxygen fugacity of formation of this kind of skarn ranges between carbon dioxide/graphite and hematite/magnetite buffers. It increases from the inside zones to the outside zones, and appears to decrease with the ore-types in the order Cu, Pb?Zn, Fe, Mo, W(Sn) ore deposits.  相似文献   

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