Cation distribution in amphiboles synthesized along the Ga analogue of the tremolite–aluminotschermakite join

 Amphiboles were synthesized from bulk compositions prepared along the join Ca_1.8Mg_5.2Si₈O₂₂(OH)₂–Ca_1.8Mg₃Ga₄Si₆O₂₂(OH)₂ hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca₂Mg₅Si₈O₂₂F₂–Ca₂Mg₃Ga₄Si₆O₂₂F₂, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: ^[6]Ga³⁺+2^[4]Ga³⁺+1/2^[A] Ca²⁺ = ^[6]Mg²⁺+2^[4]Si⁴⁺+1/2^[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001     

Thermal expansion and crystal structure of FeSi between 4 and 1173 K determined by time-of-flight neutron powder diffraction

The thermal expansion and crystal structure of FeSi has been determined by neutron powder diffraction between 4 and 1173?K. No evidence was seen of any structural or magnetic transitions at low temperatures. The average volumetric thermal expansion coefficient above room temperature was found to be 4.85(5)?×?10^?5?K^?1. The cell volume was fitted over the complete temperature range using Grüneisen approximations to the zero pressure equation of state, with the internal energy calculated via a Debye model; a Grüneisen second-order approximation gave the following parameters: θ_D=445(11)?K, V ₀=89.596(8)?ų, K ₀′=4.4(4) and γ′=2.33(3), where θ_D is the Debye temperature, V ₀ is V at T=0?K, K ₀′ is the first derivative with respect to pressure of the incompressibility and γ′ is a Grüneisen parameter. The thermodynamic Grüneisen parameter, γ_th, has been calculated from experimental data in the range 4–400?K. The crystal structure was found to be almost invariant with temperature. The thermal vibrations of the Fe atoms are almost isotropic at all temperatures; those of the Si atoms become more anisotropic as the temperature increases.     

Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

Crack damage stress as a composite function of porosity and elastic matrix stiffness in dolomites and limestones

Twenty-five uniaxial compression tests were performed to determine stress at onset of dilation, referred to herein as “the crack damage stress,” in heterogeneous dolomites and limestones. A simplified model for crack damage stress (σ_cd) is developed here using porosity, elastic modulus, Poisson's ratio and three empirical coefficients. The model shows that when porosity decreases and elastic modulus increases, σ_cd rapidly increases and approaches its maximum value. On the other hand, when porosity increases and elastic modulus decreases, σ_cd rapidly decreases and approaches its minimum value. The proposed model is validated for six heterogeneous limestone and dolomite formations which are widely distributed in Israel.     

The Port Mouton Shear Zone: intersection of a regional fault with a crystallizing granitoid pluton

The peraluminous tonalite–monzogranite Port Mouton Pluton is a petrological, geochemical, structural, and geochronological anomaly among the many Late Devonian granitoid intrusions of the Meguma Lithotectonic Zone of southern Nova Scotia. The most remarkable structural feature of this pluton is a 4-km-wide zone of strongly foliated (040/subvertical) monzogranites culminating in a narrow (10–30 m), straight, zone of compositionally banded rocks that extends for at least 3 km along strike. The banded monzogranites consist of alternating melanocratic and leucocratic compositions that are complementary to the overall composition of that part of the pluton, suggesting an origin by mineral–melt and mineral–mineral sorting. Biotite and feldspar are strongly foliated in the plane of the compositional bands. These compositional variations and foliations originated by a process of segregation flow during shearing of the main magma with a crystallinity of 55–75%. Subsequent minor brittle fracturing of feldspars, twinning of microcline, development of blocky sub-grains in quartz, and kinking of micas demonstrate overprinting by a high-temperature deformation straddling the monzogranite solidus. Small folds and late sigmoidal dykes indicate dextral movement on the shear zone. This Port Mouton Shear Zone (PMSZ) is approximately co-linear with the only outcrops of Late Devonian mafic intrusions in the area, two of which are syn-plutonic with well-developed mingling textures in the marginal tonalite of the Port Mouton Pluton. Also closely co-linear with the mafic intrusions are a granitoid dyke that extends well beyond the outer contact of the Port Mouton Pluton, a swarm of large aligned angular xenolithic slabs, a zone of thin wispy schlieren banding, a large Be-bearing pegmatite, and a breccia pipe with abundant garnetiferous metapelitic xenoliths. In various ways, the shear zone may control all of these features. The Port Mouton Shear Zone is parallel to many other NE-trending faults and shear zones in the northern Appalachians, probably related to the docking of the Meguma Zone along the Cobequid–Chedabucto Fault system.     

Petrology and geochemistry of orthoamphibolites from the Variscan metamorphic sequences of the South Tisia in Croatia – an overview with geodynamic implications

In the southern Pannonian Basin, the Variscan Barrovian- and overprinted Abukuma-type progressive metamorphic sequences of the South Tisia in Slavonian Mts. (SM) and Mt. Moslava)ka Gora (MG) are interlayered with orthoamphibolites. These sequences represent part of a disrupted Variscan belt that extends southeastwards of the Bohemian Massif through the Carpathians to the Caucasus. Orthoamphibolites contain hornblende (Mg-hornblende, tschermakite, pargasite, and edenite), plagioclase An_48-98 (MG) and An_26-35 (SM), biotite, grossular (MG) and almandine (SM) enriched garnet, diopside (MG), with accessory ilmenite, titanite, and clinozoisite. Based on major and trace element analyses and CIPW norms, these orthoamphibolites, which originally were olivine tholeiites to slightly alkalic basalts, can be correlated with tholeiites of consuming plate margins. '¹⁸O of orthoamphibolites varies from 5.8 to 7.1‰, the measured ⁸⁷Sr/⁸⁶Sr ratio from 0.70435 to 0.70665, which indicates slight continental crust contamination, and the calculated ratio from 0.70262 to 0.70535, indicating an upper mantle origin of the original basaltic melts. For associated penecontemporaneous I-type granitoids, the calculated initial ⁸⁷Sr/⁸⁶Sr ratio also have upper mantle values ranging between 0.70293 and 0.70368. Geochemical data for orthoamphibolites and the associated penecontemporaneous I-type granites, and the occurrence of alpine-type ultramafic bodies within the Barrovian sequence, indicate that they have many features in common with orogenic associations related to recent subduction-related settings. Some characteristic element ratios suggest back-arc basin environments and the Ce/K vs. Ce diagram suggests a pargasite-lherzolite source. Its partial melting gave primitive basaltic melts of olivine tholeiite to slight alkalic affinities that produced at first differentiated mafic rocks by olivine fractionation (future orthoamphibolites) and, afterwards, a strongly differentiated suite of I-type granitoids by amphibole fractionation. Magma emplacement and subsequent AFC processes took place in subduction environments preceding the main Variscan deformational metamorphic event during which orthoamphibolites were generated. This interpretation is compatible with geodynamic modeling of this part of the Paleotethys.     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.