The distribution of Fe3+ and Ga3+ between two tetrahedral sites in melilites,Ca2(Mg,Fe3+, Ga,Si)3O7     

Masahide Akasaka  Haruo Ohashi  Isamu Shinno 《Physics and Chemistry of Minerals》1986,13(3):152-155

The distribution of Fe³⁺ and Ga³⁺ between the two tetrahedral sites in three synthetic melilites has been studied by using ⁵⁷Fe Mössbauer spectroscopy. In the melilite, (Ca₂Ga₂SiO₇)₅₀ (Ca₂Fe³⁺GaSiO₇)₅₀ (mol %), the distribution of Fe³⁺ and Ga³⁺ in T1 and T2 sites is apparently random, which can be explained in terms of the electrostatic valence rule. However in the melilites, (Ca₂MgSi₂O₇)₅₂ (Ca₂Fe³⁺GaSiO₇)₄₂ (Ca₂Ga₂SiO₇)₆ and (Ca₂MgSi₂O₇)₆₂ (Ca₂Fe³⁺GaSiO₇)₃₆ (Ca₂Ga₂SiO₇)₂ (mol %), Fe³⁺ shows preference for the more ionic T1 site and Ga³⁺ for the more covalent T2 site. If the electronegativity of Ga³⁺ is assumed to be larger than that of Fe³⁺, the mode of distribution of Fe³⁺ and Ga³⁺ can be explained in terms of our previous hypothesis that a large electronegativity induces a stronger preference for the more covalent T2 site.  相似文献   

Contact metamorphosed dunite-harzburgite complex in the Chugoku district,western Japan     

Shoji Arai 《Contributions to Mineralogy and Petrology》1975,52(1):1-16

The Tari-Misaka ultramafic complex, which is emplaced into the Paleozoic sediments and thermally metamorphosed by two younger granitic masses, is divided into four zones on the basis of the mineral assemblage. They are, in order of increasing metamorphic grade: Zone I antigorite-olivine-orthopyroxene-clinopyroxene. Zone II olivine-talc. Zone III olivine-anthophyllite. Zone IV olivine-orthopyroxene. Strongly serpentinized clinopyroxene-bearing harzburgite in Zone I is similar to ordinary Alpine-type harzburgite. In Zonne II, two kinds of olivine are recognized. One is Mg-rich olivine (Fo₉₃ to Fo₉₇) with opaque inclusions and is probably a recrystallization product of serpentine with talc. The other is Fe-rich olivine (Fo₈₈ to Fo₉₃) free of opaque inclusions and is probably a relic of the primary peridotite. Olivine in Zone III and Zone IV is also relatively Mg-rich (Fo₉₁ to Fo₉₅). Chromitite in Zone IV commonly has an assemblage, olivine+cordierite+Mg-Al spinel (Mg/Mg+Fe²⁺, more than 0.9). Enstatite is rare and coexists with less magnesian Mg-Al spinel (Mg/Mg+Fe²⁺, less than 0.9). Petrological and mineralogical characters of the ultramafic rocks can be well explained by thermal metamorphism of strongly serpentinized peridotite by granitic intrusion. Metamorphic zones are consistent with the experimental results in the system MgO-SiO₂-H₂O. The assemblage olivine+cordierite indicates that the metamorphism occurred at relatively low pressures (<3kb).  相似文献   

Pumpellyites in two low grade metamorphic terranes North of Newcastle,NSW Australia     

R. Offler  C. K. Baker  J. Gamble 《Contributions to Mineralogy and Petrology》1981,76(2):171-176

Microprobe analyses of pumpellyites from rocks of variable chemistry formed under similar metamorphic conditions in two Palaeozoic, low grade metamorphic terranes show that they have an extreme range in composition (FeO^*=0.9–22.96) and that Fe²⁺Mg²⁺ and Fe³⁺Al³⁺ are the dominant substitutions. A less extreme variation in composition of pumpellyites has been noted in samples taken from a metamorphosed differentiated metadolerite. On an A1-Fe^*-Mg diagram, these pumpellyites extend through the fields of high pressure to low pressure terranes, indicating that pumpellyite compositions should be used with caution when determining metamorphic conditions.Bulk chemical composition of the host rock does not appear to be a controlling factor in determining pumpellyite compositions. Rather, intensity of alteration, particularly of opaque mineral phases, fluid chemistry and variation in oxidation potential are considered to be more important variables. Coexisting epidote and composition of the precursor mineral also appear to be important in some rocks.  相似文献   

The transition between spinel lherzolite and garnet lherzolite,and its use as a Geobarometer     

Hugh St. C. O'Neill 《Contributions to Mineralogy and Petrology》1981,77(2):185-194

The equilibrium between spinel lherzolite and garnet lherzolite has been experimentally determined in the CaO-MgO-Al₂O₃-SiO₂ system between 800° and 1,100° C. In confirmation of earlier work and predictions from thermodynamic data, it was found that theP-T slope of the reaction was close to zero, the equilibrium ranging from 16.1 kb at 800° C to 18.7 kb at 1,100° C (±0.3 kb). The addition of Cr₂O₃ to the system raised the stability field of spinel to higher pressures. It was found that the pressure at which both garnet and spinel could exist with olivine+orthopyroxene+clinopyroxene in the system CMAS ?Cr₂O₃ could best be described by the empirical relationship: $$P = P^{\text{O}} + \alpha X_{{\text{Cr}}}^{s{\text{p}}} $$ whereP ⁰ is the equilibrium pressure for the univariant reaction in the Cr₂O₃-free system,α is a constant apparently independent of temperature with a value of 27.9 kilobars, andX _Cr ^sp is the mole fraction of chromium in spinel. Use was made of the extensive literature on Mg-Fe²⁺ solid solutions to quantitatively derive the effect of Fe²⁺ on the equilibrium. The effect of other components (Fe³⁺, Na) was also considered. The equilibrium can be used as a sensitive geobarometer for rocks containing the five phases ol+opx+cpx+gt+sp, and thus provides the only independent check presently available for the more widely applicable geobarometer which uses the alumina content of orthopyroxene in equilibrium with garnet.  相似文献   

Reactions leading to the formation and breakdown of stilpnomelane in the Otago Schist, New Zealand     

Li  Essene  Peacor  & Coombs 《Journal of Metamorphic Geology》2000,18(4):393-407

Semi‐pelitic rocks ranging in grade from the prehnite–pumpellyite to the greenschist facies from south‐eastern Otago, New Zealand, have been investigated in order to evaluate the reactions leading to formation and breakdown of stilpnomelane. Detrital grains of mica and chlorite along with fine‐grained authigenic illite and chlorite occur in lower‐grade rocks with compactional fabric parallel to bedding. At higher grades, detrital grains have undergone dissolution, and metamorphic phyllosilicates have crystallized with preferred orientation (sub)parallel to bedding, leading to slaty cleavage. Stilpnomelane is found in metapelites of the pumpellyite–actinolite facies and the chlorite zone of the greenschist facies, but only rarely in the biotite zone of the greenschist facies. Illite or phengite is ubiquitous, whereas chlorite occurs only rarely with stilpnomelane upgrade of the pumpellyite‐out isograd. Chemical and textural relationships suggest that stilpnomelane formed from chlorite, phengite, quartz, K‐feldspar and iron oxides. Stilpnomelane was produced by grain‐boundary replacement of chlorite and by precipitation from solution, overprinting earlier textures. Some relict 14 Å chlorite layers are observed by TEM to be in the process of transforming to 12 Å stilpnomelane layers. The AEM analyses show that Fe is strongly partitioned over Mg into stilpnomelane relative to chlorite (K_D≈2.5) and into chlorite relative to phengite (K_D≈1.9). Modified A′FM diagrams, projected from the measured phengite composition rather than from ideal KAl₃Si₃O₁₀(OH)₂, are used to elucidate reactions among chlorite, stilpnomelane, phengite and biotite. In addition to pressure, temperature and bulk rock composition, the stilpnomelane‐in isograd is controlled by variations in K, Fe³⁺/Fe²⁺, O/OH and H₂O contents, and the locus of the isograd is expected to vary in rocks of different oxidation states and permeabilities. Biotite, quartz and less phengitic muscovite form from stilpnomelane, chlorite and phengite in the biotite zone. Projection of bulk rock compositions from phengite, NaAlO₂, SiO₂ and H₂O reveals that they lie close to the polyhedra defined by the A′FM minerals and albite. Other extended A′FM diagrams, such as one projected from phengite, NaAlO₂, CaAl₂O₄, SiO₂ and H₂O, may prove useful in the evaluation of other low‐grade assemblages.  相似文献   

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy     

G. LUCCHETTI  R. CABELLA  L. CORTESOGNO 《Journal of Metamorphic Geology》1990,8(5):539-550

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.  相似文献   

Stabilitätsbeziehungen zwischen Chlorit,Cordierit und Almandin bei der Metamorphose     

Dr. Achim Hirschberg  Helmut G. F. Winkler 《Contributions to Mineralogy and Petrology》1968,18(1):17-42

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   

The structural state of iron in oxidized vs. reduced glasses at 1 atm: A57Fe Mössbauer study     

David Virgo  Bjørn O. Mysen 《Physics and Chemistry of Minerals》1985,12(2):65-76

A general model for the structural state of iron in a variety of silicate and aluminosilicate glass compositions in the systems Na₂O-Al₂O₃-SiO₂-Fe-O, CaO-Al₂O₃-SiO₂-Fe-O, and MgO-Al₂O₃-SiO₂-Fe-O is proposed. Quenched melts with variable Al/Si and NBO/T (average number of nonbridging oxygens per tetrahedrally coordinated cation), synthesized over a range of temperatures and values of oxygen fugacity, are analyzed with⁵⁷Fe Mössbauer spectroscopy. For oxidized glasses with Fe³⁺/∑Fe>0.50, the isomer shift for Fe³⁺ is in the range ～0.22–0.33 mm/s and ～0.36 mm/s at 298 K and 77 K, respectively. These values are indicative of tetrahedrally coordinated Fe^3?. This assignment is in agreement with the interpretation of Raman, luminescence, and X-ray,K-edge absorption spectra. The values of the quadrupole splitting are ～0.90 mm/s (298 K and 77 K) in the Na-aluminosilicate glasses and compare with the values of 1.3 mm/s and 1.5 mm/s for the analogous Ca- and Mg-aluminosilicate compositions. The variations in quadrupole splittings for Fe³⁺ are due to differences in the degree of distortion of the tetrahedrally coordinated site in each of the systems. The values of the isomer shifts for Fe²⁺ ions in glasses irrespective of Fe³⁺/∑Fe are in the range 0.90–1.06 mm/s at 298 K and 1.0–1.15 mm/s at 77 K. The corresponding range of values of the quadrupole splitting is 1.75–2.10 mm/s at 298 K and 2.00–2.35 mm/s at 77 K. The temperature dependence of the hyperfine parameters for Fe²⁺ is indicative of noninteracting ions, but the values of the isomer shift are intermediate between those values normally attributable to tetrahedrally and octahedrally coordinated Fe²⁺. The assignment of the isomer-shift values of Fe²⁺ to octahedral coordination is in agreement with the results of other spectral studies. For reduced glasses (Fe³⁺/∑Fe≈<0.50), the value of the isomer shift for Fe³⁺ at both 298 K and 77 K increases and is linearly correlated with decreasing Fe³⁺/∑Fe in the range of \(f_{O_2 } \) between 10^?3 and 10^?6 atm when a single quadrupole-split doublet is assumed to represent the absorption due to ferric iron. The increase in value of the isomer shift with decreasing \(f_{O_2 } \) is consistent with an increase in the proportion of Fe³⁺ ions that are octahedrally coordinated. The concentration of octahedral Fe³⁺ is dependent on the \(T - f_{O_2 } \) conditions, and in the range of log \(f_{O_2 } \) between 10^?2.0 and 10^?5 a significant proportion of the iron may occur as iron-rich structural units with stoichiometry similar to that of inverse spinels such as Fe₃O₄, in addition to isolated Fe²⁺ and Fe³⁺ ions.  相似文献   

High-pressure phengite decomposition in the Weissenstein eclogite,Münchberger Gneiss Massif,Germany     

G. Franz  S. Thomas  D. C. Smith 《Contributions to Mineralogy and Petrology》1986,92(1):71-85

The petrography, mineral chemistry and petrogenesis of a sample from the Weissenstein eclogite, Bavaria, Germany, has been investigated. The total mineral assemblage comprises garnet, clinopyroxene_I+II, quartz, amphibole_I+II, rutile, phengite, epidote/allanite, plagioclase, biotite, apatite, pumpellyite, titanite (sphene), zircon, alkali feldspar and calcite. Textural observations combined with geothermobarometry (Fe/Mg distribution between clinopyroxene/garnet and phengite/garnet; jadeite-content of omphacite, Si-content of phengite, and An-content of plagioclase) provide indications of two different stages in the metamorphic evolution of the rock. The main phengitequartz-eclogite mineral equilibration occurred at minimum P=13–17kbar, minimum T=620±50° C; the retrograde symplectite stage (clinopyroxene_II, amphibole_II, biotite, plagioclase) occurred at P _total between 12 and 8.5 kbar. Reactions of the symplectite stage are:

1. phengite (core) + Na₂O_aq + CaO_aq=phengite (rim) + biotite + plagioclase + K₂O_aq + H₂O
2. phengite (core) + clinopyroxene_I + Na₂O_aq=phengite (rim + biotite + plagioclase + amphibole_II + SiO₂ + K₂O_aq + CaO_aq + H₂O
3. clinopyroxene_I + SiO₂ + K₂O_aq + H₂O=clinopyroxene_II + plagioclase+amphibole_II + Na₂O_aq + CaO_aq

The phengite decomposition produces H₂O, whereas the clinopyroxene decomposition consumes H₂O. The estimated P-T-conditions for the Weissenstein eclogite are in the same order of magnitude as those for other eclogite bodies from the Alps and Caledonides believed to be related to subduction processes.  相似文献   

X-ray diffraction study of Fe2+-Mg order-disorder in orthopyroxene. Some kinetic results     

S. K. Saxena  M. C. Domeneghetti  G. M. Molin  V. Tazzoli 《Physics and Chemistry of Minerals》1989,16(5):421-427

Kinetic rates of Fe²⁺-Mg disordering in three orthopyroxenes (mean value of X_Fe = Fe²⁺/(Fe²⁺+Mg) = 0.175,0.482,0.770 respectively) have been determined employing heating experiments and single crystal X-ray structural refinements. Disordering rate constants \((\vec K)\) (550800° C) for two pyroxenes are given by: ln \((\vec K)\) = 27.107(±5.177)?32062(±783)T^?1(X_Fe = 0.175) ln \((\vec K)\) = 16.142(±0.057)?18227(±423)T^?1(X_Fe = 0.770) The distribution coefficients K_D (representing a steady state of disordering Fe_M2 + Mg_M1 ? Fe_M1 + Mg_M2) are given by: ln K_D = 5.016(±0.223)-7033(±1473) T^?1(X_Fe = 0.175) ln K_D = 1.988(±0.122)-3809(±913)T^?1(X_Fe = 0.770) These distribution coefficients provide the constraint of the disordering reaction on the value of the equilibrium constant for Fe²⁺-Mg order-disorder. Until the low temperature dependence of K_D is well constrained, the calculation of cooling rates of pyroxenes and host rocks cannot be done reliably.  相似文献   

Crystal chemistry and reaction relations of piemontites and thulites from highly oxidized low grade metamorphic rocks at Vitali,Andros Island,Greece     

Thomas Reinecke 《Contributions to Mineralogy and Petrology》1986,93(1):56-76

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 Mn^tot～-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   

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer     

Kathleen M. Parkin  Bruce M. Loeffler  Roger G. Burns 《Physics and Chemistry of Minerals》1977,1(3):301-311

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.  相似文献   

Deformation‐driven,regional‐scale metasomatism in the Hamersley Basin,Western Australia     

A. J. R. White  M. Legras  R. E. Smith  P. Nadoll 《Journal of Metamorphic Geology》2014,32(4):417-433

Mafic volcanic rocks of the Fortescue Group form the lowermost stratigraphic unit of the 100,000 km² Hamersley Basin on the southern margin of the Archean Pilbara Craton, Western Australia. A regional burial metamorphic gradient extends across the basin from prehnite–pumpellyite facies in the north to greenschist facies in the south. Phase equilibria modelling of mafic rocks with the computer program thermocalc , in subsets of the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–Fe₂O₃, successfully reproduces observed metamorphic mineral assemblages, giving conditions of ~210 °C, 2 kbar in the north and 335 °C, 3.2 kbar in the south. Superimposed on this metamorphic gradient, regional‐scale metasomatism in the Fortescue Group progressively produces a suite of prehnite‐bearing and pumpellyite–quartz/epidote–quartz‐dominated assemblages. Further modelling of variably metasomatized samples consistently estimates conditions of 260–280 °C, 2.5–3 kbar across the basin. All modelled samples were likely metasomatized at approximately the same structural level, following regional deformation during the Ophthalmian orogeny. Folding during the Ophthalmian orogeny produced topographic and/or tectonic driving forces for regional‐scale fluid flow, pushing metasomatic fluid northwards across the Hamersley Basin. These new phase equilibria calculations support previous interpretations linking the Ophthalmian orogeny, fluid flow and upgrading of Hamersley iron ore deposits. We propose an extension of this fluid flow to the Fortescue Group, the metasomatism of which may have contributed a source of Fe to the Hamersley iron ore deposits.  相似文献