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1.
Previous electron paramagnetic resonance (EPR) spectroscopic study of gamma-ray-irradiated stishovite at 77 K detected an Al hole center, which was proposed to be an [O2 3−–Al3+] defect. First-principles quantum-mechanical calculations show that the unpaired spin is 85% localized on one of the six oxygen atoms at an AlO6 octahedron, while the calculated 27Al hyperfine constants are similar to those determined by EPR experiments. Theoretical results allow us to propose the Al center to represent an [AlO6]0 defect, and hole hoping among equivalent oxygen atoms is responsible for its detection only at cryogenic temperatures. Theoretical calculations also show that the diamagnetic precursors [AlO6/H+]0, [AlO6/Li+]0, and [AlO6/Na+]0 are stable in stishovite. The calculated OH bond distance and orientation are in excellent agreement with those inferred from FTIR spectra and previous theoretical calculations. The calculated [AlO6/Li+]0 and [AlO6/Na+]0 defects suggest that the monovalent cations such as Li+ and Na+ are potentially important in accommodating Al in stishovite in the lower mantle.  相似文献   

2.
The concentration of the Al and Ti paramagnetic impurity centers in pre-ore and ore-stage quartz at the Peschanka porphyry copper–molybdenum–gold deposit in the Western Chukchi Peninsula, Russia were determined using electron paramagnetic resonance spectroscopy (EPR). The [AlO 4 - /h+]0 concentration in pre-ore and ore-stage quartz varies from 29 to 124 and from 13 to 101 at. ppm, respectively. The contents of the [TiO 4 - /Li+]0 and [TiO 4 - /H+]0 centers reach 20 and 6.3 at. ppm, respectively. Pre-ore quartz associated with the formation of biotite–potassium feldspar–quartz alteration and ore-stage quartz associated with the formation of quartz–sericite rocks followed by the ore deposition differ considerably in the Ti center content, especially the [TiO 4 - /H+]0 center. The [TiO 4 - /H+]0 concentration is much higher in the pre-ore quartz (>2 at. ppm) than that in the ore-stage quartz related to copper mineralization (<2 at. ppm). The [TiO 4 - /Li+]0 concentration also decreases from pre-ore to ore-stage quartz. Taking the data we obtained into account, the formation temperature of pre-ore and ore-stage quartz estimated from a titaniumin-quartz geothermometer is 590–470°C (weighted average 520°C) and 510–310°C (weighted average 430°C), respectively. The obtained temperature range of 590 to 310°C is similar to that determined from homogenization of fluid inclusions in quartz.  相似文献   

3.
Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na2O–MgO–Al2O3–SiO2–H2O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H2O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H2O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H2O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of AlIV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [NaAAlIV]<=>[□ASi] (edenite) toward nyböite, and [Na(M4)AlVI]<=>[Mg(M4)MgVI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.  相似文献   

4.
Impurity inhomogeneities and other structural defects have been studied by means of transmission electron microscopy (TEM), X-ray microanalysis and electron paramagnetic resonance (EPR) in untreated and heat-treated quartz samples of three genetic types: hydrothermal, pegmatitic and magmatic. The impurities present are Al, Na and H2O, which occupy tetrahedral (Al3+) or interstitial (Na+, H2O) positions in the quartz lattice. Impurities form imperfections of various degrees of segregation: from point defects to micropores with a gas-liquid content. Their size, form, density and distribution in the lattice depend on the formation conditions of the quartz, the presence of dislocations and plane defects serving as sinks for the impurity atoms, and the heat treatment regime. Experimental data indicate that gas-liquid inclusions of dimensions up to some microns are the result of impurity segregation during postcrystallizational cooling. Crystalline quartz amorphizes upon electron irradiation. A model of structural water explaining experimentally observed features of this phenomenon is proposed whereby the water molecule, represented as a dipole, enters microregions of the silica lattice with a high impurity content and there forms a bond between ‘defective’ [SiO3]2? and [AlO4]5? tetrahedra. On irradiation, the Si---O donor-acceptor bonds trap nonelastically scattered electrons and are ruptured as a result. The water released by this lattice discontinuity forms microbubbles that diffuse along sinks into the larger micropores thus further increasing their volume.  相似文献   

5.
The pressure-volume-temperature-composition (PVTX) properties of H2O-CH4 were determined from the bubble point curve to 500 °C and 3 kbar for compositions ?4 mol.% CH4 using the synthetic fluid inclusion technique. H2O-CH4 inclusions were produced by loading known amounts of Al3C4 and H2O into platinum capsules along with pre-fractured and inclusion-free quartz cores. During heating the Al3C4 and H2O react to produce CH4, and the H2O-CH4 homogeneous mixture was trapped as inclusions during fracture healing at elevated temperature and pressure. The composition of the fluid in the inclusion was confirmed using the weight loss technique after the experiment and by Raman spectroscopic analysis of the inclusions.Homogenization temperatures of the inclusions were determined and the results were used to construct iso-Th lines, defined as a line connecting the formation temperature and pressure with the homogenization temperature and pressure. The pressure in the inclusion at the homogenization temperature was calculated from the Duan equation of state (EOS). The slope (ΔP/ΔT) of each iso-Th line was calculated and the results fitted to a polynomial equation using step-wise multiple regression analysis to estimate the slope of the iso-Th line as a function of the homogenization temperature and composition according to:
(ΔP/ΔT)=a+b·m+c·m4+d·(Th)2+e·m·Th+f·m·(Th)4,  相似文献   

6.
Dumortierite, generally simplified as Al7BSi3O18, was synthesized in the pure system Al2O3–B2O3–SiO2–H2O (ABSH) using gels with variable Al/Si ratios mixed with H3BO3 and H2O in known proportions as starting materials. Synthesis conditions ranged from 3 to 5 and 15 to 20 kbar fluid pressure at 650° to 880°C. On the basis of analyses, synthetic dumortierite shows relatively narrow homogeneity ranges with regard to Al/Si which, however, vary as a function of pressure: at low pressures (3–5 kbar) Al/Si is 2.77–2.94 versus 2.33–2.55 at high pressures (15–20 kbar). Outside of these homogeneity limits, dumortierite was found to coexist with quartz or corundum, depending on the starting composition. Whereas synthetic dumortierite invaribly contains 1.0 boron atom per formula unit (p.f.u.) based on 18 oxygens, the water contents vary drastically as a function of pressure and temperature (1.32–2.30 wt.% H2O or 0.85–1.47 H p.f.u.). H2O is an essential component in dumortierite. Structural formulae based on complete chemical analyses of the dumortierites synthesized reveal that there is invariably an Si-deficiency against the ideal number of 3.0 p.f.u. In the calculation procedure used here, this deficiency is balanced by assuming tetrahedral Al. The remaining Al, taken to occupy the octahedral sites, is always below the ideal number of 7.0 p.f.u. Charge-balancing the structure with the hydrogen found analytically leads to two different mechanisms of H incorporation: (1) 3H+ + octahedral vacancy for Al[6]; (2) H+ + tetrahedral Al for Si[4]. Dumortierite synthesized at high fluid pressure contains little Al[4] and, thus, little H+ of type 2; its hydrogen is predominantly present as type 1. Conversely, dumortierite formed at low fluid pressures is high in Al[4] and hydrogen type 2. The amounts of hydrogen type 1 in low-pressure dumortierites decrease with rising temperatures of synthesis. Typical structural formulae are: (Al6.670.33)[Al0.49Si2.51–O13.53(OH)1.47](BO3) for a low-pressure product, and (Al6.680.32)[Al0.09Si2.91O13.94(OH)1.06](BO3) for a high-pressure product. Independently of the synthesis conditions, dumortierite was found always to be orthorhombic, with b0/a0 deviating slightly, but significantly from the valid for hexagonal lattice geometry. As a function of increasing Al/Si in the synthetic crystals, their a0, c0, and V0 rise, whereas b0 decreases. Thus b0/a0 decreases most sensitively with rising Al/Si and also with growing Al[4]. More experimentation is required before the compositional variations of dumortierite found here can be applied successfully to geothermobarometry of natural rocks.  相似文献   

7.
The formation mechanism of Al30O8(OH)56(H2O)2618+ (Al30) has been investigated by the density functional theory based on the supermolecule model and kinetic analysis on the 27Al nuclear magnetic resonance (NMR) experimental results in monitoring Al30 synthesis process. The theoretical chemistry calculations on the four possible schemes show that δ-Na-Al13 is the reasonable intermediate followed by the substitution of Na with Al to form δ-Al14, and Na+ plays an important role in stabilizing the intermediate (δ-Na-Al13) in the transformation. The kinetic analysis on the 27Al NMR experimental data indicates that ε-Al13 decomposes and isomerizes in the formation of Al30, while Al monomers facilitate the decomposition of ε-Al13 and so the isomerization of ε-isomers to δ-isomers effectively. The favorable formation mechanism of Al30 includes three steps: (1) ε-Al13 decomposes and rearranges into the isomer δ-Al13; (2) Na+ reacts with δ-Al13 to stabilize the intermediate δ-Na-Al13, followed by Al monomers replacing Na to form δ-Al14; (3) δ-Al14 reacts with the Al monomers in the solution to finally form Al30. Both Al monomers and Na+ are important in the transformation. Al monomers are the basic building units and helpful to the isomerization while Na+ can well stabilize the isomer δ-Al13 to yield intermediate δ-Na-Al13. The results also show that other isomers of ε-Al13 (β-Al13 and α-Al13) form in the formation of Al30, and their calculated 27Al NMR tetrahedral resonance shifts are consistent with the experimental 27Al NMR tetrahedral signals in the preparation process of Al30.  相似文献   

8.
In the Ultevis District, Northern Sweden, viridine occurs in a potassium rich, microcline-bearing leptite together with quartz, plagioclase, phlogopite, opaques, and a retrogradely formed muscovite. The formation of viridine in this rock may be described by a dealkalization process of microcline, in which opaque minerals are involved. A diffusion of K+ and H2O out of the centres of viridine formation and of H+ into these localities, which is a prerequisite of such type of reaction, may have been favoured by a contemporaneous migmatization of the rock, since the granite-like melts can be regarded as sinks for potassium and water. The following decomposition of viridine is initiated by the reverse reaction. Texturally this is indicated by small microcline seams along the contacts between viridine and quartz grains. The final alkalization of the viridine-quartz assemblage to form muscovite reflects increasing K+/H+-ratios and H2O-contents of the vapor phase and/or decreasing temperatures. The potassium and water amounts necessary for the viridine decomposition reactions may have been generated by the cooling of the granitic liquids. An intergrowth of sillimanite and the muscovite can be described by a degenerated reaction. It can be interpreted as giving way to an equilibration of the alumosilicates und the actual metamorphic conditions, that is here P, T, , a k +, a h + and a Mn 3+.The viridine investigated has the lowest Mn-contents recorded so far for andalusite-type minerals with viridine optics (1.3–2.2 mol-% Mn2SiO5-component). Since no andalusite with lower Mn-contents occurs in the rock and since no other Al2SiO5-phase formed at this metamorphic stage it may be assumed that the incorporation of manganese stabilizes the andalusite structure under the P-, T-, –, a k +-, a h +- and a Mn 3+-conditions verified in this particular leptite.The temperature of viridine formation is estimated to be about 600 ° C, the decomposition of viridine +quartz into the muscovite-sillimanite assemblage may have happened between 650–500 ° C at 6–2.5 kb.  相似文献   

9.
The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a 29Si hyperfine structure (A ~12.6 MHz) and an 27Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The 29Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The 27Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These 29Si and 27Al hyperfine data, together with published theoretical results on peroxy radicals in SiO2 as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al3+ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al3+ ion corresponds closely to the diamagnetic precursor to the [AlO4]0 center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

10.
Natural quartz crystals coming from Madagascar, Angola, Brazil, and Spain were studied by EPR after β irradiation in order to characterise the paramagnetic centres due to impurities, and examine in which way their relative proportion could constitute a useful criterion for origin researches. In all our samples, EPR experiments revealed germanium centres [GeO4/M+]° with M = Li or Na, aluminium ones [AlO4/h]° and two titanium centres ([TiO4/H+]° and [TiO4/M+]°) also appeared, except for samples coming from Spain. The comparison of the relative concentrations of paramagnetic species led us on to draw diagrams that allowed distinguishing the origins of the studied samples using only EPR spectra. To cite this article: M. Duttine et al., C. R. Geoscience 334 (2002) 949–955.  相似文献   

11.
In the Tuoshi oilfield,located in the Cenozoic Jianghan Basin of southeastern China ,there have been found hydrocarbon reservoirs hosted in lacustrine sandstones of the Eogene Xingouzui Formation.The main diagenetic features identified in these sandstones include the dissolution of detrital K-feldspar and albite grains,the precipitation of quartz as overgrowths and /or cements ,and the precipitation and /or transformation of clay minerals.These diagenetic features were interpreted to have occurred in early,intermediate and late stages,based on the burial depth.The kinetics of fluid-mineral reactions and the concentrations of aqueous species au each stage of diagenesis were simulated numerically for these lacustrine sandstones,using a quasi-sta-tionary state approximation that incorporates simultaneous chemical reactions in a time-space continuum.During the early diagenetic stage,pore fluid was weakly acidic,which resulted in dissolution of K-feldspar and albite and,therefore,led to the release of K^ ,Na^ ,Al^3 and SiO2(aq) into the diagenetic fluid.The increased K^ ,Na^ ,Al^3 and SiO2(aq) concentrations in the diagenetic fluid caused the precipitation of quartz,kaolinite and illite.At the beginning of the intermediate diagenetic stage the concentration of H^ was built up due to the decomposition of organic matter,which was responsible for further dissolution of K-feldspar and albite and pre-cipitation of quartz,kaolinite,and illite.During the late diagenetic stage,the pore fluid was weakly alkaline,K-feldspar became stable and was precipitated with quartz and clay minerals.When the burial depth was greater than 3000 m,the pore fluids became supersaturated with respect to allbite,but undersaturated with respect to quartz,resulting in the precipitation of albite and the dissolution of quartz.The diagenetic reactions forecasted in the numerical modeling closely matched the diagenet-ic features identified by petrographic examination, and therefore,can help us to gain a better understanding of the diagenetic processes and associated porosity evolution in sandstone reservoirs.  相似文献   

12.
The chemical interaction between fluorine and highly polymerized sodium aluminosilicate melts [Al/(Al+Si)= 0.125–0.250 on the join NaAlO2-SiO2] has been studied with Raman spectroscopy. Fluorine is dissolved to form F– ions that are electrically neutralized with Na+ or Al3+. There is no evidence for association of fluorine with either Si4+ or Al3+ in four-fold coordination and no evidence of fluorine in six-fold coordination with Si4+ in these melt compositions. Upon solution of fluorine nonbridging oxygens are formed and are a part of structural units with nonbridging oxygen per tetrahedral cations (NBO/T) about 2 and 1. The proportions of these two depolymerized units in the melts increase systematically with increasing F/(F+O) at constant Al/(Al+Si) and with decreasing Al/(Al+Si) at constant F/(F+O). Depolymerization (increasing NBO/T) of silicate melts results from a fraction of aluminum and alkalies (in the present study; Na+) reacting to form fluoride complexes. In this process an equivalent amount of Na+ (orginally required for Al-3+charge-balance) or Al3+ (originally required Na+ to exist in tetrahedral coordination) become network-modifiers.The structural data have been used to develop a method for calculating the viscosity of fluorine-bearing sodium aluminosilicate melts at 1 atm. Where experimental viscosity data are available, the calculated and measured values are within 5% of each other.A method is also suggested by which the liquidus phase equilibria of fluorine-bearing aluminosilicate melts may be predicted. In accord with published experimental data it is suggested, for example, that — on the basis of the determined solubility mechanism of fluorine in aluminosilicate melts — with increasing fluorine content of feldspar-quartz systems, the liquidus boundaries between aluminosilicate minerals (e.g., feldspars) and quartz shift away from silica.  相似文献   

13.
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly.  相似文献   

14.
 The charge compensation problem for Si−Al substitution in Brazilian natural quartz is investigated in relation to γ-irradiation darkening response and impurity contents evaluated by atomic absorption spectrometry and infrared absorption spectroscopy. Al+3 in as-grown natural quartz is compensated by Li+ and H+ to form Al−Li and Al−OH centers. The content ratios (Al−Li)/(Al−OH) and Li/(broad OH band) depend on the environmental conditions of crystal growth and influence the formation of Al-hole centers due to γ-irradiation. Al−OH centers are the dominant Al-related centers in quartz from hydrothermal origin while Al−Li centers are dominant for that of pegmatitic origin. The formation of Al-hole centers is little in quartz with a high content of broad OH band which is from low temperature hydrothermal origin. Received May 23, 1995 / Revised, accepted May 8, 1996  相似文献   

15.
Experiments up to water pressures of 21 kbar have been undertaken to bracket the reactions chlorite + quartz = talc + kyanite + H2O, chlorite + quartz = talc + cordierite + H2O, and talc + kyanite + quartz = cordierite ± H2O by reversed runs in the system MgO-Al2O3-SiO2-H2O (MASH). These reaction curves intersect at an invariant point (IP1) at PH2O = 6.4 ± 0.2 kbar and a temperature of 624 ± 4°C. The curve of the chlorite + quartz breakdown to talc + kyanite + H2O at water pressures above 6.4 kbar shows a negative dP/dT, with the slope decreasing with rising pressure, whereas the slope of the breakdown curve to talc + cordierite + H2O at water pressures is clearly positive. The composition of the chlorite solid solution reacting with quartz has been estimated to be approximately Mg4.85Al1.15[Al1.15Si2.85O10](OH)8 over the entire pressure range investigated. The composition of the talc solid solution forming by the breakdown of chlorite + quartz appears to be Mg2.94Al0.06[Al0.06Si3.94O10](OH)2 at PH2O = 2kbar. With increasing pressure, the Al content of talc decreases, reaching a value of about 0.06 atoms per formula unit at P,H2O = 21 kbar. As a consequence of the new experimental data, the existing phase topologies of the MASH-system and K2O-MASH-system have been revised. For example, the invariant point IP1 and the univariant reaction curve kyanite + talc + H2O = chlorite + cordierite are stable. For this reason, the development of medium- to high-temperature metamorphic rocks compositionally approximating the MASH-system must be reconsidered. The whiteschists from Sar e Sang, Afghanistan, are treated as an example. The application of the present experimental data to metamorphic rocks of more normal composition requires the examination of the influence of further components. This leads to the conclusion that the introduction of Fe2+ into magnesian chlorite extends its stability field in the presence of quartz by 10°-15°C in comparison with pure Mg-chlorite.  相似文献   

16.
Summary Results of a multidisciplinary study on quartz concentrates (mineralogically separated) and etched concentrates (stoichiometric quartz) from three locations at Allchar (Macedonia) are presented. The investigation of quality and composition of these quartz samples is of great interest because the same material has been previously used as monitor for 26Al Acceleration Mass-Spectrometry (AMS) erosion rate estimates. Two genetically different types of quartz are distinguished in the studied samples which petrologically can be described as hydrothermally altered dacites or quartz latites; i.e. volcanic (QV) and hydrothermal (QH) quartz with relative proportions of QH:QV around 3:2. QH is genetically related to the Allchar Sb–As–Tl–S mineralization having very high Sb (85–785 ppm), As (7.6–78 ppm) and (Tl 3.3–4.0 ppm) contents. This type of quartz is also characterized by very high Li (129–138 ppm), Al (2424–2520 ppm) and Ti (153–219 ppm) concentrations. QV appears to be much less enriched in trace elements having Al and K contents ranging from 0 to 280 ppm and from 50 to 85 ppm, respectively. 26Al AMS measurements were done on the samples containing two genetically different types of quartz but this had no effects on the interpretation and erosion rate determinations. However, the extremely high Al concentrations in the analyzed quartz have generally negative effects, mainly by decreasing 26Al/27Al ratios and thus causing an increase of the detection limit. The disagreement between the results of 26Al AMS analyses and quantitative geomorphologic data for one location is probably caused by different geographical position with respect to the direction of cosmic rays.  相似文献   

17.
The compositional characteristics of many geochemical systems which involve the interaction of natural aqueous solutions with minerals and gases are conveniently described using the following thermodynamic components: Cl?, SO4=, HS?, CO3=, H+, Na+, K+, Ca++, Mg++, Fe++, Zn++, Cu+, Al+++, SiO2 and H2O. A set of mass balance and mass action equations equal in number to the number of components plus the number of saturated minerals (and gases) is defined for a specified temperature, pressure and bulk composition. The mass balance equations include terms for minerals, gases and the molalities of aqueous complexes and dissociated species. This set of non-linear equations can be solved with the aid of a computer using'a Newton-Raphson technique. The calculation takes account of aqueous ion complexing, oxidation-reduction equilibria, activity coefficients, non-unit water activity and solid solutions. The use of H+, SO4=, HS? and H2O as components allows straightforward treatment of processes involving oxidation-reduction, evaporation, boiling and changes of total aqueous H+ due to hydrolysis, mineral reaction or temperature change. One product of this approach is a technique for calculating pH at high temperature from measurement of pH at room temperature.By linking a series of discrete overall heterogeneous equilibrium calculations in which incremental changes of bulk composition, temperature or pressure are made, dynamic geochemical processes can be modeled. Example calculations for two such processes are given. These are the heating of seawater from 25° to 300°C and the isothermal irreversible reaction of rhyolite with an aqueous solution at 250°C.  相似文献   

18.
The occurrence of high-pressure (HP) blueschists within the central Qiangtang terrane of northern Tibet has a significant bearing on plate-suturing processes. In order to contribute to the ongoing debate on whether the central Qiangtang metamorphic belt represents an in situ suture within the Qiangtang terrane, we examined lawsonite- and glaucophane-bearing blueschists from the northwest Qiangtang area (84° 10′–85° 30′ E, 34°10′–34° 45′ N). All studied rocks are metapelites, metasandstones, or metabasalts, characterized by lawsonite + glaucophane + phengite, lawsonite + glaucophane + epidote + albite + quartz, or glaucophane + phengite + quartz assemblages. The meta-mafic rocks contain very high TiO2 and low Al2O3 contents. They are typified by abundant ferromagnesian trace elements, and an absence of Eu anomalies and Nb–Ta deletions; all the above features indicate that these mafic rocks represent oceanic island basalt (OIB) protoliths. Most of the metasediments contain high SiO2, moderate Al2O3 + K2O, and low TiO2 + Na2O. They display high CIA (chemical index of alteration) values (74% ± 5%) and distinctly negative Eu anomalies (Eu/Eu* = 0.64 ± 0.05). This, along with their high field strength elemental characteristics, indicates that they were deposited in a passive continental margin environment, intercalated with OIB-type basalts. We estimate the peak metamorphic conditions for these blueschists as T = 330–415°C and P = 9–11.5 kbar. This HP event occurred at ca. 242 Ma, indicated by a well-defined 40Ar/39Ar plateau age for glaucophane. Retrograde metamorphism occurred at T = 280–370°C, P = 6.5–9.5 kbar, t = ca. 207 Ma (40Ar/39Ar dating of phengite). Therefore, a cold subduction (geotherm ～8°C/km) attended the passive continental margin during the Triassic when the eastern Qiangtang collided with the western Qiangtang. The northwest Qiangtang HP metamorphic belt is an extension of the central Qiangtang metamorphic belt that defines the suture between eastern and western Qiangtang, and indicates an anticlockwise, diachronous closure of the Shuanghu Palaeo-Tethys.  相似文献   

19.
Single-crystal W-band electron paramagnetic resonance (EPR) spectra of an electron-irradiated quartz, measured at room temperature, 110 and 77 K, disclose three previously reported hole centers (#1, G and an ozonide radical). The W-band EPR spectra of these three centers clearly resolve six magnetically nonequivalent sites each, whereas previous X- and Q-band EPR studies reported Centers #1 and the ozonide radical to consist of only three symmetry-related components and interpreted them to reside on twofold symmetry axes in the quartz structure. The calculated g matrices of Center #1 and the ozonide radical show that deviations from twofold symmetry axes are <10°, which are probably attributable to distortion related to neighboring charge compensating ions. The W-band EPR spectra of Center G not only result in improved g matrices but also allow quantitative determination of the nuclear hyperfine (A) and quadrupole (P) matrices of its 27Al hyperfine structure that was incompletely resolved before. In particular, the g-maximum and g-minimum principal axes of Center G are approximately along two pairs of O–O edges of the SiO4 tetrahedron, while the unique A principal axis is approximately along a Si–Si direction. These new spin-Hamiltonian parameters suggest that Center G most likely involves trapping of a hole between two oxygen atoms related to a silicon vacancy and stabilized by an Al3+ ion in the neighboring tetrahedron (hence an O2n−–Al3+ defect, where n is either 1 or 3).  相似文献   

20.
Trace element contents and distributions in authigenic quartz cement in deeply buried (2500–4000 m) Haushi Group sandstones from wells in Oman have been investigated in order to determine the factors that control trace element uptake during precipitation.Scanning electron microscope-cathodoluminescence images show well developed growth zones within the quartz cement, which correlate with chemical zonations observed in electron microprobe Al distribution maps. The most abundant trace elements are Al (50–3000 μg g?1), Li (1–100 μg g?1), Na (1–40 μg g?1), and Ge (0.3–5 μg g?1) with a strong linear correlation between Li and Al and a weaker one between Ge and Al. The molar concentration of Li (+ Na) accounts only for ~ 15% of the charge compensation for Al3+ substitution of Si4+. Though H was not measured in this study, these data indicate a major role of H in charge balancing Al3+. The samples belong to the same stratigraphic unit and have similar petrography, but show considerable variability in absolute trace element concentrations between different wells. This variability does not correlate with either sample depth or temperature and shows no regional pattern, but seems to reflect petrophysical and tectonic differences within the sedimentary basin.Petrographic observations of the cogenetic mineral assemblages and hydrochemical modelling indicate that a change from the equilibrium assemblage quartz–kaolinite (–dolomite) to quartz–illite (–dolomite) reflects a decrease in the CO2 concentration and concurrent variations of the Al concentration. It is concluded that changes in the CO2 concentrations are responsible for fluctuations in fluid Al concentrations and thus likely also in the investigated quartz cements.  相似文献   

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