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1.
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 (KD≈2.5) and into chlorite relative to phengite (KD≈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   

2.
Quantitative X‐ray maps of composition from a chlorite, K‐white mica, albite, quartz and garnet bearing thin section from a Sambagawa blueschist facies metapelite were combined with a multi‐equilibrium calculation method to calculate a PT‐Fe3+/Fe2+‐deformation map at the millimetre scale. The studied sample was chosen because elongated chlorite crystallization tails (pressure shadows) rimmed by phengite are present, which is an appropriate assemblage for the quantification of the PT evolution. Chlorite temperature and Fe3+ content maps were calculated by successive iterations for each pixel analysis of Fe3+ until convergence of the four chlorite‐quartz‐H2O equilibria that can be written using the Fe‐ and Mg‐amesite, clinchlore, daphnite and sudoite chlorite end‐members. The calculated map of Fe2+/Fe3+ in chlorite is in good qualitative agreement with the in situ mapping of this ratio using XANES (X‐ray absorption near edge structure) techniques. The temperature map indicates that high temperature chlorite zones with low Fe3+ contents alternate with lower temperature zones and higher Fe3+ contents in the crystallization tail. Late fractures perpendicular to the elongation axis of the tail are filled by very low temperature chlorite (<250 °C) showing Fe3+/Fetotal up to 0.4. Groups of chlorite and mica pixels were then identified based on compositional and structural criteria, and a PT‐deformation map was calculated using representative analyses of these groups. The calculated PT‐deformation map suggests that in contrast to chlorite, the composition of most mica did not change significantly during exhumation. Mica reequilibrated in late EW shear bands only. EW shearing was already active at 0.1 GPa, 500 °C, which corresponds to the peak temperature (and probably pressure) conditions, at reduced redox conditions. The intensity of deformation probably decreased with decrease in temperature to ~350–400 °C. At this temperature, a second main deformation event corresponding to a further EW stretching occurred and was still active below 250 °C and more oxidizing conditions. These results indicate that the scale at which PT data can be obtained is now close to the scale of observation of structural geologists. A close link between deformation and mineral reaction is therefore possible at the microscopic scale, which provides information about the relationship between deformation and mineral reactivity, the modalities of deformation with time and the PT conditions at which it occurred.  相似文献   

3.
In this study, we have deduced the thermal history of the subducting Neotethys from its eastern margin, using a suite of partially hydrated metabasalts from a segment of the Nagaland Ophiolite Complex (NOC), India. Located along the eastern extension of the Indus‐Tsangpo suture zone (ITSZ), the N–S‐trending NOC lies between the Indian and Burmese plates. The metabasalts, encased within a serpentinitic mélange, preserve a tectonically disturbed metamorphic sequence, which from west to east is greenschist (GS), pumpellyite–diopside (PD) and blueschist (BS) facies. Metabasalts in all the three metamorphic facies record prograde metamorphic overprints directly on primary igneous textures and igneous augite. In the BS facies unit, the metabasalts interbedded with marble show centimetre‐ to metre‐scale interlayering of lawsonite blueschist (LBS) and epidote blueschist (EBS). Prograde HP/LT metamorphism stabilized lawsonite + omphacite (XJd = 0.50–0.56 to 0.26–0.37) + jadeite (XJd = 0.67–0.79) + augite + ferroglaucophane + high‐Si phengite (Si = 3.6–3.65 atoms per formula unit, a.p.f.u.) + chlorite + titanite + quartz in LBS and lawsonite + glaucophane/ferroglaucophane ± epidote ± omphacite (XJd = 0.34) + chlorite + phengite (Si = 3.5 a.p.f.u.) + titanite + quartz in EBS at the metamorphic peak. Retrograde alteration, which was pervasive in the EBS, produced a sequence of mineral assemblages from omphacite and lawsonite‐absent, epidote + glaucophane/ferroglaucophane + chlorite + phengite + titanite + quartz through albite + chlorite + glaucophane to lawsonite + albite + high‐Si phengite (Si = 3.6–3.7 a.p.f.u.) + glaucophane + epidote + quartz. In the PD facies metabasalts, the peak mineral assemblage, pumpellyite + chlorite + titanite + phengitic white mica (Si = 3.4–3.5 a.p.f.u.) + diopside appeared in the basaltic groundmass from reacting titaniferous augite and low‐Si phengite, with prehnite additionally producing pumpellyite in early vein domains. In the GS facies metabasalts, incomplete hydration of augite produced albite + epidote + actinolite + chlorite + titanite + phengite + augite mineral assemblage. Based on calculated TM(H2O), T–M(O2) (where M represents oxide mol.%) and PT pseudosections, peak PT conditions of LBS are estimated at ~11.5 kbar and ~340 °C, EBS at ~10 kbar, 325 °C and PD facies at ~6 kbar, 335 °C. Reconstructed metamorphic reaction pathways integrated with the results of PT pseudosection modelling define a near‐complete, hairpin, clockwise PT loop for the BS and a prograde PT path with a steep dP/dT for the PD facies rocks. Apparent low thermal gradient of 8 °C km?1 corresponding to a maximum burial depth of 40 km and the hairpin PT trajectory together suggest a cold and mature stage of an intra‐oceanic subduction zone setting for the Nagaland blueschists. The metamorphic constraints established above when combined with petrological findings from the ophiolitic massifs along the whole ITSZ suggest that intra‐oceanic subduction systems within the Neotethys between India and the Lhasa terrane/the Karakoram microcontinent were also active towards east between Indian and Burmese plates.  相似文献   

4.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)4+3CrO2−4+4OH+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=AB/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated.  相似文献   

5.
The stability of pumpellyite + actinolite or riebeckite + epidote + hematite (with chlorite, albite, titanite, quartz and H2O in excess) mineral assemblages in LTMP metabasite rocks is strongly dependent on bulk composition. By using a thermodynamic approach (THERMOCALC), the importance of CaO and Fe2O3 bulk contents on the stability of these phases is illustrated using P–T and P–X phase diagrams. This approach allowed P–T conditions of ~4.0 kbar and ~260 °C to be calculated for the growth of pumpellyite + actinolite or riebeckite + epidote + hematite assemblages in rocks containing variable bulk CaO and Fe2O3 contents. These rocks form part of an accretionary wedge that developed along the east Australian margin during the Carboniferous–Triassic New England Orogen. P–T and P–X diagrams show that sodic amphibole, epidote and hematite will grow at these conditions in Fe2O3‐saturated (6.16 wt%) metabasic rocks, whereas actinolite and pumpellyite will be stable in CaO‐rich (10.30 wt%) rocks. With intermediate Fe2O3 (~3.50 wt%) and CaO (~8.30 wt%) contents, sodic amphibole, actinolite and epidote can coexist at these P–T conditions. For Fe2O3‐saturated rocks, compositional isopleths for sodic amphibole (Al3+ and Fe3+ on the M2 site), epidote (Fe3+/Fe3+ + Al3+) and chlorite (Fe2+/Fe2+ + Mg) were calculated to evaluate the efficiency of these cation exchanges as thermobarometers in LTMP metabasic rocks. Based on these calculations, it is shown that Al3+ in sodic amphibole and epidote is an excellent barometer in chlorite, albite, hematite, quartz and titanite buffered assemblages. The effectiveness of these barometers decreases with the breakdown of albite. In higher‐P stability fields where albite is absent, Fe2+‐Mg ratios in chlorite may be dependent on pressure. The Fe3+/Al and Fe2+/Mg ratios in epidote and chlorite are reliable thermometers in actinolite, epidote, chlorite, albite, quartz, hematite and titanite buffered assemblages.  相似文献   

6.
Alpine metamorphism, related to the development of a metamorphic core complex during Cretaceous orogenic events, has been recognized in the Veporic unit, Western Carpathians (Slovakia). Three metamorphic zones have been distinguished in the metapelites: 1, chloritoid + chlorite + garnet; 2, garnet + staurolite + chlorite; 3, staurolite + biotite + kyanite. The isograds separating the metamorphic zones have been modelled by discontinuous reactions in the system K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH). The isograds are roughly parallel to the north‐east‐dipping foliation related to extensional updoming along low‐angle normal faults. Thermobarometric data document increasing PT conditions from c. 500 °C and 7–8 kbar to c. 620 °C and 9–10 kbar, reflecting a coherent metamorphic field gradient from greenschist to middle amphibolite facies. 40Ar/39Ar data obtained by high spatial resolution in situ ultraviolet (UV) laser ablation of white micas from the rock slabs constrain the timing of cooling and exhumation in the Late Cretaceous. Mean dates are between 77 and 72 Ma; however, individual white mica grains record a range of apparent 40Ar/39Ar ages indicating that cooling below the blocking temperature for argon diffusion was not instantaneous. The reconstructed metamorphic PTt path is ‘clockwise’, reflecting post‐burial decompression and cooling during a single Alpine orogenic cycle. The presented data suggest that the Veporic unit evolved as a metamorphic core complex during the Cretaceous growth of the Western Carpathian orogenic wedge. Metamorphism was related to collisional crustal shortening and stacking, following closure of the Meliata Ocean. Exhumation was accomplished by synorogenic (orogen‐parallel) extension and unroofing in an overall compressive regime.  相似文献   

7.
The pumpellyite–actinolite facies proposed by Hashimoto is defined by the common occurrence of the pumpellyite–actinolite assemblage in basic schists. It can help characterize the paragenesis of basic and intermediate bulk compositions, which are common constituents of various low-grade metamorphic areas. The dataset of mutually consistent thermodynamic properties of minerals gives a positive slope for the boundary between the pumpellyite–actinolite and prehnite–pumpellyite facies in PT space. In the Sanbagawa belt in Japan, the mineral parageneses of hematite-bearing and -free basic schists, as well as pelitic schists have been well documented. The higher temperature limit of this facies is defined by the disappearance of the pumpellyite+epidote+actinolite+chlorite assemblage in hematite-free basic schists with XFe3+ of epidote around 0.20–0.25 and the appearance of epidote+actinolite+chlorite assemblage with XEpFe3+≤0.20. In hematite-bearing basic schists, there is a continuous change of paragenesis to higher grade, epidote–glaucophane or epidote–blueschist facies. In pelitic schists, the albite+lawsonite+chlorite assemblage does occur but only rarely, and its assemblage cannot be used to determine the regional thermal structure. The lower temperature equivalence of the pumpellyite–actinolite assemblage is not observed in the field. The Mikabu Greenstone complex and the northern margin of the Chichibu complex, which are located to the south of the Sanbagawa belt, are characterized by clinopyroxene+chlorite or lawsonite+actinolite assemblages, which are lower temperature assemblages than the pumpellyite+actinolite assemblage. These three metamorphic complexes belong to the same subduction-metamorphic complex. The pumpellyite–actinolite facies or subfacies can be useful to help reveal the field thermal structure of metamorphic complexes  相似文献   

8.
In the present study, the modified Sverjensky–Molling equation, derived from a linear-free energy relationship, is used to predict the Gibbs free energies of formation of crystalline phases of α-MOOH (with a goethite structure) and α-M2O3 (with a hematite structure) from the known thermodynamic properties of the corresponding aqueous trivalent cations (M3+). The modified equation is expressed as ΔG0f,MVX=aMVXΔG0n,M3++bMVX+βMVXγM3+, where the coefficients aMVX, bMVX, and βMVX characterize a particular structural family of MvX (M is a trivalent cation [M3+] and X represents the remainder of the composition of solid); γ3+ is the ionic radius of trivalent cations (M3+); ΔG0f,MVX is the standard Gibbs free energy of formation of MvX; and ΔG0n,M3+ is the non-solvation energy of trivalent cations (M3+). By fitting the equation to the known experimental thermodynamic data, the coefficients for the goethite family (α-MOOH) are aMVX=0.8838, bMVX=?424.4431 (kcal/mol), and βMVX=115 (kcal/mol.?), while the coefficients for the hematite family (α-M2O3) are aMVX=1.7468, bMVX=?814.9573 (kcal/mol), and βMVX=278 (kcal/mol.?). The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases (i.e. phases that are thermodynamically unstable and do not occur at standard conditions) within the isostructural families of goethite (α-MOOH) and hematite (α-M2O3) if the standard Gibbs free energies of formation of the trivalent cations are known.  相似文献   

9.
An Early Palaeozoic (Ordovician ?) metamudstone sequence near Wojcieszow, Kaczawa Mts, Western Sudetes, Poland, contains numerous metabasite sills, up to 50 m thick. These subvolcanic rocks are of within-plate alkali basalt type. Primary igneous phases in the metabasites, clinopyroxene (salite) and kaersutite, are veined and partly replaced by complex metamorphic mineral assemblages. Particularly, the kaersutite is corroded and rimmed by zoned sodic, sodic–calcic and calcic amphiboles. The matrix is composed of actinolite, pycnochlorite, albite (An ≤ 0.5%), epidote (Ps 27–33), titanite, calcite, opaques and, occasionally, biotite, phengite and stilpnomelane. The sodic amphiboles are glaucophane to crossite in composition with NaB from 1.9 to 1.6. They are rimmed successively by sodic–calcic and calcic amphiboles with compositions ranging from magnesioferri-winchite to actinolite. No compositions between NaB= 0.92 and NaB= 1.56 have been ascertained. The textures may be interpreted as representing a greenschist facies overprint on an earlier blueschist (or blueschist–greenschist transitional) assemblage. The presence of glaucophane and no traces of a jadeitic pyroxene + quartz association indicate pressures between 6 and 12 kbar during the high-pressure episode. Temperature is difficult to assess in this metamorphic event. The replacement of glaucophane by actinolite + chlorite + albite, with associated epidote, allows restriction of the upper pressure limit of the greenschist recrystallization to <8 kbar, between 350 and 450°C. The mineral assemblage representing the greenschist episode suggests the P–T conditions of the high-pressure part of the chlorite or lower biotite zone. The latest metamorphic recrystallization, under the greenschist facies, may have taken place in the Viséan.  相似文献   

10.
The Ordovician Kellerjochgneiss (Schwaz Augengneiss) is a polymetamorphic orthogneiss-bearing unit and is part of the Austroalpine basement nappes north of the Tauern Window. Within the Kellerjochgneiss a small, strongly deformed metapegmatite dike occurs. The pegmatite crosscuts the gneiss discordantly and contains the mineral assemblage muscovite 1,2+plagioclase+K-feldspar+chlorite+quartz+garnet 1 (Alm67–76Andr0.9–2Sps17–28Prp0.4–5)+garnet 2 (Grs36–46Alm24–32Andr8–21Sps15–17Prp0–1)±stilpnomelane±biotite±clinozoisite. The magmatic protolith assemblage is comprised of relict K-feldspar, quartz and garnet 1. Textural observations indicate that biotite and muscovite cores (muscovite 1) are either part of the magmatic- or an earlier (Variscan?) metamorphic assemblage. Geothermobarometry of the metapegmatite was done on the latest-stage (Eo-Alpine) mineral assemblage garnet 2+muscovite 2+chlorite+stilpnomelane+plagioclase+quartz. Calculations of H2O-absent intersections in the system [KCNFMAS] with the multi-equilibrium program THERMOCALC v.3.1 yielded PT estimates of 4.4 to 6.7 kbar and 321°C to 376°C. Calculations of the PT conditions by using the assemblage muscovite 2+chlorite+stilpnomelane+quartz yielded slightly higher pressures of 6.4 to 7.2 kbar at temperatures of 310–325°C. Correlating these PT data with geochronological data from the neighbouring lithologies (Kellerjochgneiss, Innsbruck Quartzphyllite, Wildschönau Schists) and with structural investigations from these units indicate that the PT estimates obtained in this investigation represent the Eo-Alpine metamorphic overprint. Hence, these unusual rocks provide important information on the Eo-Alpine PT conditions since most samples studied from the investigated Austroalpine basement nappes north of the Tauern Window rarely contain mineral assemblages suitable for geothermobarometry.  相似文献   

11.

Using adsorption of organic matter (OM) on diethylaminoethyl cellulose (DEAE-cellulose) in the dynamic mode, OM is divided into autochthonous and allochthonous. Based on the experiments on BOD kinetics and OM division into components, the kinetic parameters of autochthonous and allochthonous OM transformation are established for the first time (kaut = 0.013, kall = 0.0013 day–1 at t =20°C). The activation parameters of transformation for autochthonous OM (ΔH# = 75.6 kJ/mol, ΔS# =–116.5 J/(mol K), and ΔG# = 108.3 J/mol) and allochthonous OM (ΔH# = 66.1 kJ/mol, ΔS# =–149.1 J/(mol K), and ΔG# = 108.0 J/mol) are calculated by the Arrhenius equation.

  相似文献   

12.
Strain localization within shear zones may partially erase the rock fabric and the metamorphic assemblage(s) that had developed before the mylonitic event. In poly‐deformed basements, the loss of information on pre‐kinematic phases of mylonites hinders large‐scale correlations based on tectono‐metamorphic data. In this study, devoted to a relict unit of Variscan basement reworked within the nappe stack of the Northern Apennines (Italy), we investigate the possibility to reconstruct a complete pressure (P)temperature (T)–deformation (D) path of mylonitic micaschist and amphibolite by integrating microstructural analysis, mineral chemistry and thermodynamic modelling. The micaschist is characterized by a mylonitic fabric with fine‐grained K‐white mica and chlorite enveloping mica‐fishes, quartz, and garnet pseudomorphs. Potassic white mica shows Mg‐rich cores and Mg‐poor rims. The amphibolite contains green amphibole+plagioclase+garnet+quartz+ilmenite defining S1 with a superposed mylonitic fabric localized in decimetre‐ to centimetre‐scale shear zones. Garnet is surrounded by an amphibole+plagioclase corona. Phase diagram calculations provide P–T constraints that are linked to the reconstructed metamorphic‐deformational stages. For the first time an early high‐P stage at >11 kbar and 510°C was constrained, followed by a temperature peak at 550–590°C and 9–10 kbar and a retrograde stage (<475°C, <7 kbar), during which ductile shear zones developed. The inferred clockwise P–T–D path was most likely related to crustal thickening by continent‐continent collision during the Variscan orogeny. A comparison of this P–T–D path with those of other Variscan basement occurrences in the Northern Apennines revealed significant differences. Conversely, a correlation between the tectono‐metamorphic evolution of the Variscan basement at Cerreto pass, NE Sardinia and Ligurian Alps was established.  相似文献   

13.
PENG GAO 《Sedimentology》2012,59(6):1926-1935
A recently developed bedload equation (Abrahams & Gao, 2006) has the form ib = ωG3˙4, where ib is the immersed bedload transport rate, ω is the stream power per unit area, G = 1?θc/θ, θ is the dimensionless shear stress and θc is the associated threshold value for the incipient motion of bed grains. This equation has a parsimonious form and provides good predictions of transport rate in both the saltation and sheetflow regimes (i.e. flows with low and high θ values, respectively). In this study, the equation was validated using data independent of those used for developing it. The data represent bedload of identical sizes transported in various steady, uniform, fully rough and turbulent flows over plane, mobile beds. The equation predicted ib quite well over five orders of magnitude. This equation was further compared with six classic bedload equations and showed the best performance. Its theoretical significance was subsequently examined in two ways. First, based on collision theory, the parameter G was related to the ratio of grain‐to‐grain collisions to the total collisions including both grain‐to‐grain and grain‐to‐bed collisions, Pg by Pg = G2, suggesting that G characterizes the dynamic processes of bedload transport from the perspective of granular flow, which partly accounts for the good performance of the equation. Moreover, examining the ability of two common equations to predict bedload in gravel‐bed rivers revealed that G can also be used to simplify equations for predicting transport capacities in such rivers. Second, a simple dimensionless form of the equation was created by introducing B = ib/ω. The theoretical nature of the term B was subsequently revealed by comparing this equation with both the Bagnold model and two commonly used parameters representing dimensionless bedload transport rates.  相似文献   

14.
57Fe Mössbauer spectra are presented for synthetic cation-deficient Fe2TiO4 and FeCr2O4 spinel particles (<1μm) at various temperatures. The spectra of ferrimagnetic cation-deficient Fe2TiO4 show characteristic features due to relaxation because of superparamagnetism and spin relaxation in the temperature range 5–294 K. At 5 K and 78 K, a superposition of at least two sextets is observed which appear to arise from Fe3+ onA-sites (Fe A 3+ andB-sites (Fe B 3+ ) of the spinal lattice with magnetic hyperfine fields at 5 K ofB hf ((Fe B 3+ )≈47.5 T andB hf (Fe B 3+ )≈51.0 T, respectively. Cation-deficient FeCr2O4 particles reveal at 78 K a fieldB hf (Fe3+)≈46.9 T and exhibit relaxation spectra as a consequence of superparamagnetism in the temperature range 80 K - ~300 K. At 294 K, quadrupole splitting Δ(Fe A 3+ )=0.92 mm/s and isomer shift δ(Fe A 3+ )=0.29 mm/s (relative to metallic Fe) are measured. For both compounds the magnetic hyperfine fieldsB hf are discussed in terms of supertransferred hyperfine fields involving vacancies and in the case of cation-deficient Fe2TiO4 also diamagnetic Ti4+ neighbours of the Fe ions.  相似文献   

15.
At Deobhog, migmatitic gneisses and granulites of the Eastern Ghats Belt are juxtaposed against a cratonic ensemble of banded augen gneiss, amphibolite and calcsilicate gneiss, intruded by late hornblende granite and dolerite. In the migmatitic gneiss unit, early isoclinal folds (syn‐D1M and D2M) are reoriented along N–S‐trending and E‐dipping shear planes (S3M), with (S1M–S3M) intersection lineations having steep to moderate plunges. The near‐peak PT condition was syn‐D3M (≥900 °C, 9.5 kbar), as inferred from syn‐D3M Grt+Opx‐bearing leucosomes in mafic granulites, and from thermobarometry on Grt (corona)–Opx/Cpx–Pl–Qtz assemblages. The PT values are consistent with the occurrence of Opx–Spr–Crd assemblages in spatially associated high‐Mg–Al pelites. A subsequent period of cooling followed by isothermal decompression (800–850 °C, c. 7 kbar) is documented by the formation of coronal garnet and its decomposition to Opx+Pl symplectites in mafic granulites. Hydrous fluid infiltration accompanying the retrograde changes is manifested in biotite replacing Opx in some lithologies. The cratonic banded gneiss–granite unit also documents two phases of isoclinal folding (D1B & D2B), with the L2B lineation girdle different from the lineation spread in the migmatitic gneiss unit. Calcsilicate gneiss (Hbl–Pl–Cpx–Scap–Cal) and amphibolite (Hbl–Pl±Grt±Cpx) within banded gneisses record syn‐D2B peak metamorphic conditions (c. 700 °C, 6.5 kbar), followed by cooling (to c. 500 °C) manifested in the stabilization of coronal clinozoisite–epidote. The D3B shear deformation post‐dates granite and dolerite intrusions and is characterized by top‐to‐the‐west movement along N–S‐trending, E‐dipping shear planes. Deformation mechanisms of quartz and feldspar in granites and banded gneisses and amphibole–plagioclase thermometry within shear bands in dolerites document an inverted syn‐D3B thermal gradient with temperature increasing from 350 to 550 °C in the west to ≥700 °C near the contact with the migmatitic gneiss unit. The thermal gradient is reflected in the stabilization of chlorite after hornblende in S3B shears to the west, and post‐D2B neosome segregation along D3B folds and shears to the east. The contrasting lithologies, early structures and peak metamorphic conditions in the two units indicate unconnected pre‐D3PT –deformation histories. The shared D3 deformation in the two units, the syn‐D3 inverted thermal gradient preserved in the footwall cratonic rocks and the complementary cooling and hydration of the hanging wall granulites across the contact are attributed to westward thrusting of ‘hot’ Eastern Ghats granulites on ‘cool’ cratonic crust. It is suggested that the Eastern Ghats migmatitic gneiss unit is not a reworked part of the craton, but a para‐autochthonous/allochthonous unit emplaced on and amalgamated to the craton.  相似文献   

16.
A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter ΔGO= Mz+(c) characterizing the oxygen affinity of the cation Mz+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity ΔGO= Mz+(c) between any two consecutive cations. The ΔGO= Mz+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between ΔGO= Mz+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as ΔGO= Mz+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.  相似文献   

17.
Abstract The Pennine rocks exposed in the south-east Tauern Window, Austria, contain mineral assemblages which crystallized in the mid-Tertiary ‘late Alpine’regional metamorphism. The pressure and temperature conditions at the thermal peak of this event have been estimated for rocks at four different structural levels using a variety of published and thermochemically derived geobarometers and geothermometers. The results are: (a) In the garnet+chlorite zone, 2–5 km structurally above the staurolite+biotite isograd: T= 490.50°C, P= 7° 1 kbar; (b) Within 0.5 km of the staurolite+biotite isograd: T= 560±300C, P=7.1 kbar; (c) In the staurolite+biotite zone, c. 2.5 km structurally below the staurolite+biotite isograd: T= 610±30°C, P=7.6±1.2 kbar; (d) In the staurolite+biotite zone, 3–4 km structurally below the staurolite+biotite isograd: T= 630±40°C, P= 6.6±1.2 kbar. The pressure estimates imply that the total thickness of overburden above the basement-cover interface in the mid-Tertiary was c. 26.4 km. This overburden can only be accounted for by the Austro-Alpine units currently exposed in the vicinity of the Tauern Window, if the Altkristallin (the ‘Middle Austro-Alpine’nappe) was itself buried beneath an ‘Upper Austro-Alpine’nappe or nappe-pile which was 7.4 km thick at that time. The occurrence of epidote + margarite + quartz pseudomorphs after lawsonite in garnet, indicates that part of the Mesozoic Pennine cover sequence in the south-east Tauern experienced blueschist-facies conditions (T<450°C, P<12 kbar) in early Alpine times. Evidence from the central Tauern is used to argue that the blueschist-facies imprint post-dated the main phase of tectonic thickening (D1A) and was thus a direct consequence of continental collision. Combined oxygen-isotope and fluid-inclusion studies on late-stage veins, thought to have been at lithostatic pressure and in thermal equilibrium with their host rocks during formation, suggest that they crystallized from aqueous fluids at 1.1±0.4 kbar and 420.20°C. Early Alpine, late Alpine and vein-formation P–T constraints have been used to construct a P–T path for the base of the Mesozoic cover sequence in the south-east Tauern Window. The prograde part of the P–T path, between early and late Alpine metamorphic imprints, is unlikely to have been a smooth curve and may well have had a low dP/dT overall; the decompression (presumably due to erosion) which occurred immediately before the thermal peak and possibly also earlier in the Tertiary, was probably partly or completely cancelled by the effects of early- to mid-Tertiary (D2A) tectonic thickening. The thermal peak of metamorphism was followed by a phase of almost isothermal decompression, which implies a period of rapid uplift in the middle Tertiary. The peak metamorphic P–T estimates are compared with the solutions of England's (1978) one-dimensional conductive thermal model of the Eastern Alps, and are shown to be consistent with the idea that the late Alpine metamorphism was caused by tectonic burial of the Pennine Zone beneath the Austro-Alpine nappes in the absence of extraneous heat sources, such as large intrusions, at depth.  相似文献   

18.
Abstract Three reactions are calibrated as geothermobarometers for garnet–orthopyroxene–plagioclase–quartz assemblages, namely: 1/2 ferrosilite + 1/3 pyrope ± 1/2 enstatite + 1/3 almandine (A): ferrosilite + anorthite ± 2/3 almandine + 1/3 grossularite + quartz (B); and enstatite + anorthite ± 2/3 pyrope + 1/3 grossularite + quartz (C). The internally consistent geothermobarometers based on reactions (A), (B) and (C) are calibrated from experimental data only. The thermodynamic parameters of reaction (A) are derived from published experimental data in the FMAS system (n= 104) in the range 700–1400°C and 5–50 kbar, while those for reaction (B) are derived by summation of the existing reversed experimental data of the mineral equilibria: ferrosilite ± fayalite + quartz (D) and anorthite + fayalite ± 2/3 almandine + 1/3 grossularite (E). The retrieved thermodynamic parameters for reactions (A), (B) and (C) are, respectively: (ΔH0, cal) -3367 ± 209, -2749 ± 350 and +3985 ± 545; (ΔS0, cal K?1) -1.634 ± 0.163, -8.644 ± 0.298 and -5.376 ± 0.391; and (ΔV01,298, cal bar?1) -0.024, -0.60946 and -0.5614. On a one-cation basis, the derived Margules parameters of the ternary Ca–Fe–Mg in garnet are: WFe–Mg= -1256 + 1.0 (~0.23) T(K), WMg–Fe= 2880 -1.7 (~0.13) T(K), WCa–Mg= 4047 (~77) -1.5 T(K), WMg–Ca= 1000 (~77) -1.5 T(K), WCa–Fe= -723 + 0.332 (~0.02) T(K), WFe–Ca= 1090, (cal) and the ternary constant C123= -4498 + 1.516 (~0.265) T(K) cal (subregular solution model of non-ideal mixing); and Fe–Mg–Al in orthopyroxene: WFe–Mg= 948 (~200) -0.34 (~0.10) T(K), WFe–Al= -1950 (~500) and WMg–Al= 0 (cal) (regular solution model of non-ideal mixing). The anorthite activity in plagioclase is calculated by the ‘Al-avoidance’model of subregular Ca–Na mixing commonly used for geobarometry based on reactions (B) and (C). When the geothermobarometers are applied to garnet–orthopyroxene–plagioclase–quartz assemblages (n= 45) of wide compositional range from the Precambrian South Indian granulites, temperature ranges of 690–860°C (X= 760 ± 45°C) and pressure ranges of 5–10 kbar were obtained. The P–T values were estimated simultaneously and there is no difference in the pressure calculated from PMg (reaction C) and PFe (reaction B). In the existing calibrations this difference is 1 kbar or more. Furthermore, there is no compositional dependence of the ln K of the experimental data in the FMAS (n= 104) and the CFMAS (n= 78) systems at different temperatures and the estimated temperatures of the South Indian granulites.  相似文献   

19.
Variations in chemistry and related physical properties of sheet silicates in the Ouégoa district with metamorphic grade are investigated. Weakly metamorphosed rocks prior to the crystallization of lawsonite contain phengite (d 006=3.317–3.323 Å), chlorite and occasionally paragonite while interstratified basaltic sills contain chlorite, minor phengite and stilpnomelane. Pyrophyllite crystallizes before lawsonite in some metamorphosed acid tuffs and is also stable in the lawsonite zone. Paragonite, phengite and chlorite appear to be stable through the sequence from weakly metamorphosed rocks into high-grade “eclogitic” schists and gneisses. Optical, chemical and some X-ray diffraction data is given for representative sheet silicates. Electron probe analyses of 55 phengites, 21 paragonites, 57 chlorites, 12 vermiculites, 2 stilpnomelanes, and 2 chloritoids are presented in graphical form. All K-micas analysed are consistently phengitic (3.29–3.55 Siiv ions per formula unit) and show limited solid solution with paragonite (4 to 13% Pa). The K∶Na ratio of the phengite is strongly dependant on the assemblage in which it occurs; the amount of phengite component and its Fe∶Mg ratio depends on bulk-rock composition. Phengites from acid volcanics have the highest Fe∶Mg ratio, highest phengite component and β refractive indices. Phengites from basic volcanics and metasediments of the epidote zone have the lowest Fe∶Mg ratio. Phengites from lawsonite-zone metasediments have intermediate Fe∶Mg ratios. The phengites show a small decrease in phengite component with increasing metamorphic grade. d 006 for phengites varied from 3.302 to 3.323 Å but at least in the lawsonite and epidote zones appears to reflect composition and had little systematic variation with metamorphic grade; phengites from very low-grade rocks showed the longest values of d 006. Paragonite shows almost no phengite-type substitution and only limited solid solution (4–12%) with muscovite. All paragonites (6) and most phengites (20) which have been examined are 2M1 polymorphs; one Fe2+-phengite appears to be a 1M polymorph. The chemistry of chlorites closely reflects parent-rock chemistry. Chlorites from metasediments have distinctly higher Fe/(Fe+Mg) ratios than chlorites from basic igneous rocks; chlorites from the lawsonite and lawsonite-epidote transitional zone metasediments have the highest Fe/(Fe+Mg) ratios. In metabasalts Fe/(Fe+Mg) ratios appear to reflect individual variations in bulk-rock chemistry and show no direct correlation with metamorphic grade. There is little difference in Al/(Si+Al) ratio between chlorites from sediments and basic igneous rocks although in both lithologies the chlorites from the epidote zone appear to be slightly more aluminous. Fe-rich chlorites of the lawsonite zone metasediments have been altered by a process involving leaching of Fe and Mg and introduction of alkalies to a brown pleochroic Fe-vermiculite. Chemical and physical data for this vermiculite are given. The decrease in Fe/(Fe+Mg) ratio in chlorites and phengites on passing from the lawsonite to the epidote zone can be correlated with the crystallization of Fe-rich epidote and almandine in the epidote zone. Elemental partitioning between coexisting minerals has shown Ti to be partitioned into phengite, while Fe and Mn are strongly partitioned into chlorite. When either stilpnomelane or chloritoid coexists with phengite or chlorite, Fe and Mn are slightly enriched in the stilpnomelane or chloritoid relative to the chlorite.  相似文献   

20.
Alpine deformation in the Grimsel granodiorite (Aar massif, Central Alps) at greenschist facies conditions (6.5 ± 1 kbar for 450°C ± 25°C) is characterized by the development of a network of centimetre to decametre localized shear zones that surround lenses of undeformed granodiorite. Localization of deformation is assumed to be the result of a first stage of extreme localization on brittle precursors (nucleation stage) followed by a transition to ductile deformation and lateral propagation into the weakly deformed granodiorite (widening stage). A paradox of this model is that the development of the ductile shear zone is accompanied by the crystallization of large amounts of phyllosilicates (white mica and chlorite) that maintains a weak rheology in the localized shear zone relative to the host rock so that deformation is localized and prevents shear zone widening. We suggest that chemical processes, and more particularly, the metamorphic reactions and metasomatism occurring during re‐equilibration of the metastable magmatic assemblage induced shear zone widening at these P–T–X conditions. These processes (reactions and mass transfer) were driven by the chemical potential gradients that developed between the thermodynamically metastable magmatic assemblage at the edge of the shear zone and the stable white mica and chlorite rich ultramylonite formed during the first stage of shear zone due to localized fluid infiltration metasomatism. PT and chemical potential projections and sections show that the process of equilibration of the wall rocks (μ–μ path) occurs via the reactions: kf + cz + ab + bio + MgO + H2O = mu + q + CaO + Na2O and cz + ab + bio + MgO + H2O = chl + mu + q + CaO + Na2O. Computed phase diagram and mass balance calculations predict that these reactions induce relative losses of CaO and Na2O of ~100% and ~40% respectively, coupled with hydration and a gain of ~140% for MgO. Intermediate rocks within the strain gradient (ultramylonite, mylonite and orthogneiss) reflect various degrees of re‐equilibration and metasomatism. The softening reaction involved may have reduced the strength at the edge of the shear zone and therefore promoted shear zone widening. Chemical potential phase diagram sections also indicate that the re‐equilibration process has a strong influence on equilibrium mineral compositions. For instance, the decrease in Si‐content of phengite from 3.29 to 3.14 p.f.u, when white mica is in equilibrium with the chlorite‐bearing assemblage, may be misinterpreted as the result of decompression during shear zone development while it is due only to syn‐deformation metasomatism at the peak metamorphic condition. The results of this study suggest that it is critical to consider chemical processes in the formation of shear zones particularly when deformation affects metastable assemblages and mass transfer are involved.  相似文献   

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