Chemistry, reaction mechanisms and micro-structures during retrograde metamorphism of gedrite-biotite-plagioclase bearing rocks from Bergslagen, south-central Sweden

The Proterozoic rhyolitic volcanics constituting the foot-wall rocks in the Stollberg ore-field, Bergslagen, south-central Sweden, locally contain gedrite altered to chlorite and serpentine, biotite altered to chlorite and plagioclase altered to epidote.

The intergrowths between the host gedrite and the chlorite/serpentine inclusions are oriented with the a^* of gedrite parallel to the c^* of serpentine and chlorite. The biotite has been altered to chlorite by brucitization of both the K-interlayer and talc-like layer. In both cases the net change in volume during chloritization is small.

The assumption that Al is conserved during alteration of gedrite and biotite agrees very well with the micro-structures and orientation relations observed by transmission electron microscopy. Normalizing the chlorite to 1.00 mole, the overall chemical change that took place during the retrograde metamorphism of the Stollberg rocks can be written as: 0.84Ged+0.14Bio+0.65Mg+4.76H₂O+0.42H=1.00Chl+0.57Alb+0.72Fe+0.01Na+0.12K+0.01Ti+0.05Mn+0.95H₄SiO₄ The reaction results in ca 9% increase in volume for the solid phases. Thus, a slightly acidic Mg-rich fluid started the reaction and, upon leaving the system, the metasomatic fluid was enriched in Na, Fe, K, and Si.     

Scales of equilibrium and disequilibrium during cleavage formation in chlorite and biotite-grade phyllites, SE Vermont

Detailed electron microprobe analyses of phyllosilicates in crenulated phyllites from south‐eastern Vermont show that grain‐scale zoning is common, and sympathetic zoning in adjacent minerals is nearly universal. We interpret this to reflect a pressure‐solution mechanism for cleavage development, where precipitation from a very small fluid reservoir fractionated that fluid. Multiple analyses along single muscovite, biotite and chlorite grains (30–200 μm in length) show zoning patterns indicating Tschermakitic substitutions in muscovite and both Tschermakitic and di/trioctahedral substitutions in biotite and chlorite. Using cross‐cutting relationships and mineral chemistry it is shown that these patterns persist in cleavages produced at metamorphic conditions of chlorite‐grade, chlorite‐grade overprinted by biotite‐grade and biotite‐grade. Zoning patterns are comparable in all three settings, requiring a similar cleavage‐forming mechanism independent of metamorphic grade. Moreover, the use of ⁴⁰Ar/³⁹Ar geochronology demonstrates this is true regardless of age. Furthermore, samples with chlorite‐grade cleavages overprinted by biotite porphyroblasts suggest the closure temperatures for the diffusion of Al, Si, Mg and Fe ions are greater than the temperature of the biotite isograd (>～400 °C). Parallel and smoothly fanning tie lines produced by coexisting muscovite–chlorite, and muscovite–biotite pairs on compositional diagrams demonstrate effectively instantaneous chemical equilibrium and probably indicate simultaneous crystallization. These results do not support theories suggesting cleavages form in fluid‐dominated systems. If crenulation cleavages formed in systems in which the chemical potentials of all major components are fixed by an external reservoir, then the compositions of individual grains defining these cleavages would be uniform. On the contrary, the fine‐scale chemical zoning observed probably reflects a grain‐scale process consistent with a pressure‐solution mechanism in which the aqueous activities of major components are defined by local dissolution and precipitation. Thus the role of fluids was probably limited to one of catalysing pressure‐solution and fluids apparently did not drive cleavage development.     

鄂尔多斯盆地纳岭沟铀矿床绿泥石特征及地质意义

纳岭沟铀矿床位于鄂尔多斯盆地北部,具有明显的后期热液作用的特征,矿体空间展布主要受控于绿色-灰色砂岩的过渡界面,与绿泥石化的蚀变砂岩关系密切。通过对纳岭沟铀矿床不同颜色砂岩中的绿泥石进行详细的岩相学研究和电子探针化学成分分析,依据绿泥石的成因与共生矿物的关系,识别出绿泥石主要的3种类型:填隙物型绿泥石,片状与黄铁矿共生型绿泥石以及黑云母蚀变型绿泥石;同时通过绿泥石的Fe-Si图解确定了纳岭沟铀矿床不同颜色砂岩中的绿泥石主要为铁镁绿泥石和密绿泥石。根据Al/(Fe+Mg+Al)-Mg/(Fe+Mg)的关系图解确定出不同颜色砂岩中的绿泥石具有铁镁质流体和泥质两种来源,通过绿泥石中主要阳离子与镁的关系图解和计算得出的绿泥石形成温度共同确定出绿泥石是多期次的中低温热液流体作用的产物。综合研究表明,纳岭沟铀矿床的绿泥石形成至少经历了温度稍高的还原性流体和温度稍低的氧化性流体等两个期次的流体作用,稍高温的还原性流体与成矿关系更为重要。与绿泥石形成有关的热液流体作用不仅带入了部分铀,还促进了铀的活化和运移。     

Authigenic layer silicate minerals in borehole Elmore 1, Salton Sea Geothermal Field,California, USA

A combined petrographic/X-ray/electron microprobe and energy dispersive system investigation of sandstone cuttings from borehole Elmore # 1 near the center of the Salton Sea Geothermal Field has revealed numerous regular variations in the composition, texture, mineralogy and proportions of the authigenic layer silicate minerals in the temperature interval 185° C (411.5 m depth) to 361° C (2,169 m). At temperatures near 190° C, dolomite/ankerite+calcite-bearing sandstones contain an illite/mixed layer phase with 10% expandable layers (dolomite/ankerite zone). In shale, the percentage of expandable layers in the mixed layer phase changes from 10–15% at 185° C to 5% at 210° C (494 m). In the interval 250° C (620 m) to 325° C (1,135 m), the calcite+pyrite+epidote-bearing sandstones contain a layer silicate assemblage of chlorite and illite (chlorite-calcite zone). In the shallower portions of this metamorphic zone, the illite contains 0–5% expandable layers, while at depths greater than 725 m (275° C) it is completely free of expandable layers. On increasing temperature, the white mica shows regular decreases in Si^IV, Mg and Fe, and increase in Al^IV, Al^VI, and interlayer occupancy, as it changes gradually from fine-grained illite (=textural sericite) to coarse-grained recrystallized phengitic white mica. In the same interval, chlorite shows decreases in Al^VI and octahedral vacancies and an increase in total Mg+Fe. The sandstones range from relatively unmodified detrital-textured rocks with porosities up to 20% and high contents of illite near 250° C to relatively dense hornfelsic-textured rocks with trace amounts of chlorite and phengite and porosities near 5% at 325° C. Numerous complex reactions among detrital (allogenic) biotite, chlorite, and muscovite, and authigenic illite and chlorite, occur in the chlorite-calcite zone.Biotite appears, and calcite disappears, at a temperature near 325° C and a depth of 1,135m. The biotite zone so produced persists to 360° C in sandstone, at which temperature orthoclase disappears and andradite garnet appears at a depth near 2,155 m. Throughout the biotite zone and into the garnet zone, the biotite undergoes compositional changes that are very similar to those observed in illite/phengite in the chlorite-calcite zone, including increases in interlayer occupancy, Al^IV, Al^VI, and Ti, and decreases in F^–, Si^IV, and Mg/Fe_t+Mg, on increasing temperature. Biotite thus changes from a siliceous, K-deficient biotite at the biotite isograd to a typical low-grade metamorphic biotite at temperatures near 360° C. Minor amounts of talc appear with biotite at the biotite isograd in sandstone, while actinolite appears in both sandstone and shale at temperatures near 340° C (1,325 m). Chlorite completely disappears from sandstone at temperatures of approximately 350° C (1,500 m), and diminishes abruptly in amount in the more chloritic shales at the same depth.     

Biotite dissolution and Cr(VI) reduction at elevated pH and ionic strength

The effects of elevated pH, ionic strength, and temperature on sediments in the vadose zone are of primary importance in modeling contaminant transport and understanding the environmental impact of tank leakage at nuclear waste storage facilities like those of the Hanford site. This study was designed to investigate biotite dissolution under simulated high level waste (HLW) conditions and its impact on Cr(VI) reduction and immobilization. Biotite dissolution increased with NaOH concentrations in the range of 0.1 to 2 mol L^-1. There was a corresponding release of K, Fe, Si, and Al to solution, with Si and Al showing a complex pattern due to the formation of secondary zeolite minerals. Dissolved Fe concentrations were an order of magnitude lower than the other elements, possibly due to the formation of green rust and Fe(OH)₂. The reduction of Cr(VI) to Cr(III) also increased with increased NaOH concentration. A homogeneous reduction of chromate by Fe(II)_aq released through biotite dissolution was probably the primary pathway responsible for this reaction. Greater ionic strengths increased biotite dissolution and consequently increased Fe(II)_aq release and Cr(VI) removal. The results indicated that HLW would cause phyllosilicate dissolution and the formation of secondary precipitates that would have a major impact on radionuclide and contaminant transport in the vadose zone at the Hanford site.     

与湘南白腊水锡矿床有关的骑田岭花岗岩的绿泥石化研究

湘南白腊水锡矿床位于骑田岭燕山期黑云母花岗岩中。绿泥石化是这一含矿花岗岩中常见的热液蚀变现象,对采自
钻孔的岩石样品研究发现,花岗岩的绿泥石化程度变化较大。本文选择三组绿泥石化蚀变程度显著不同的花岗岩样品进行
研究,探讨了与锡成矿密切相关的含矿花岗岩的绿泥石化作用。研究表明,不同程度绿泥石化花岗岩中的绿泥石,在产出
形式与化学成分上均表现出一系列明显不同的特征。依据绿泥石产出形式、化学成分、绿泥石化花岗岩地球化学等特征认
为,绿泥石对花岗岩造岩矿物的交代顺序为：角闪石、黑云母→斜长石、钾长石→石英;绿泥石形态特征的变化一方面与
绿泥石成分有关,另一方面与被其交代的造岩矿物晶体结构有关;花岗岩绿泥石化越强烈,全岩的烧失量和Zn含量就越
高,原岩的Cl丢失到蚀变流体中去的量也越多。随着花岗岩绿泥石化程度的加强,其绿泥石的主要成分含量会呈现出规律
性的变化。绿泥石的Si含量在绿泥石化过程中逐渐减少;长石遭受破坏溶解后释放出的Al在厘米尺度范围内发生迁移与再
分配,引起绿泥石Al含量的升高;Fe从热液中带入,蚀变花岗岩中绿泥石矿物含量的多少与水-岩反应体系中Fe的多少有
关;形成绿泥石所需的Mg主要来源于花岗岩暗色矿物内Mg的释放与再分配;Mn则主要由外部流体带入。     

Crystal chemistry of iron in natural grandidierites: an X-ray absorption fine-structure spectroscopy study

 Fe–K edge XAFS spectra (pre-edge, XANES and EXAFS) were collected for eight grandidierites from Madagascar and Zimbabwe, as well as for Fe(II) and Fe(III) model compounds (staurolite, siderite, enstatite, berlinite, yoderite, acmite, and andradite). The pre-edge spectra for these samples are consistent with dominantly 5-coordinated ferrous iron. The analysis of the XANES and EXAFS spectra confirms that Fe(II) substitutes for Mg(II) in grandidierite, with a slight expansion of the local structure around Mg by ∼2%. In addition, ferric iron was also detected in some samples [5–10 mol% of the total Fe or 500–1100 ppm Fe(III)]. Based on theoretical calculations of the EXAFS region, Fe(III) appears to be located in the 5-coordinated sites of Mg(II) or in the most distorted 6-coordinated sites of Al (depending on the sample studied). Special attention is therefore required when using grandidierite as a model for ferrous iron in C_3v geometry, because of the possible presence of an extra contribution related to Fe(III). This additional contribution enhances significantly the Fe–K pre-edge integrated area [+40% for 1000 ppm Fe(III)]. Therefore, only a few grandidierite samples can be used as a robust structural model for the study of the Fe(II) coordination in glasses and melts. Received: 26 June 2000 / Accepted: 19 February 2001     

Distribution of Fe in the octahedral sheet of trioctahedral micas by polarized EXAFS

The distribution of Fe atoms within the octahedral sheet of a series of trioctahedral micas has been investigated by polarized Fe K-edge EXAFS spectroscopy. Single crystals have been oriented in the X-ray beam with the layer plane at 35° with respect to the electric field vector. At this “magic angle”, contributions to the EXAFS spectrum of nearest cation shells are equal to those recorded on a completely disoriented powder. The average number of Fe and Mg cations surrounding each Fe atom has been determined and compared with those deduced from NMR spectra. It is shown that the distribution of Fe atoms is not random, the deviation from this distribution depending on the fluorine content. The agreement between these independent results proves the reliability of the structural information deduced from EXAFS and NMR spectra as well as the usefulness of these two methods in analyzing the local distribution of cations in minerals.     

Far infrared spectra of hydrous layer silicates

Observation of major bands seen in infrared spectra of 26 phyllosilicates (23 of which were produced in the laboratory) are reported for wave numbers from 50 to 280 cm^?1. Substitutions in the various structural sites (interlayer, tetrahedral and octahedral) permit one to identify the ions which contribute to the vibrations which give rise to bands in the infrared spectra. No attempt is made to assign vibrational modes or specific vibrational types. Using the following ion substitutions, OH-OD; Na-K-Sr-Mg-Ca; Si-Ge; Al-Ga; Mg-Co-Ni-Fe, it is apparent that in the 7 Å chlorite (amesite and chrysotile), kaolinite, pyrophyllite, aluminous dioctahedral mica, aluminous smectites and trioctahedral micas it is not possible to attribute any low frequency bands as being dominated by interlayer ion stretch vibrations (alkali ions). The cations which participate in the vibrators responsible for the dominant modes observed then seem to be Si and Al. This does not exclude the existence of interlayer ion stretch modes in these spectral regions, however they could not be identified. In the materials studied only a few bands can be attributed to hydroxyl-related vibrations and little influence is seen for octahedrally coordinated ions in dioctahedral minerals. It is important to note that the lowest frequency bands (80–140 cm^?1) are apparently dominated by vibrations in the network and especially to the Si-O part of the structure. Low frequency bands are however most apparent in charged layer structures, i.e. micas and smectites.     

Microstructures and compositional variation in the intravolcanic bole clays from the eastern Deccan volcanic province: Palaeoenvironmental implications and duration of volcanism

Clay minerals associated with intra-volcanic bole horizons of varied colours and thicknesses contain montmorillonite, halloysite and kaolinite, show distinct microstructures and microaggregates. In kaolinite, Fe³⁺ ions substitute for Al³⁺ at octahedral sites. Most of these clays are dioctahedral type, show balance between net layer and interlayer charges. The interstratified illite — smectite (I/S) mixed layers containing variable proportions of montmorillonite. Illite contains sheet-like, well oriented microaggregates. The parallel stacks of chlorite sheets show chlorite/smectite (C/S) mixed layers. Progressive enrichment of Fe and depletion of Al ions with the advancement of kaolinization process is observed. High order of structural and compositional maturity observed in these bole clays, indicate long hiatus between the two volcanic episodes.     

Simultaneous incorporation of Mn and Al in the goethite structure

Two series of (Al,Mn)-substituted goethites were synthesized from ferrihydrite made in alkaline media, with different Al/Mn mole ratios ([Al + Mn]/Fe molar ratio up to 0.12). Powder X-ray diffraction and extended X-ray absorption fine structure (EXAFS) techniques were used to assess the structural characteristics of the simultaneous substitution in goethite. XRD patterns revealed that all the obtained solids remain in a goethite-like structure. Rietveld refinement of X-ray diffraction data indicates that the increasing Mn substitution and consequent decrease of Al substitution causes an increase in the unit cell volume. This change is accompanied by the increment of the various Me-Me distances. XANES spectra at the Al and Mn K-edge confirm the octahedral coordination of Al and the trivalent oxidation state of the Mn ion in all the synthesized samples. EXAFS spectra at the Fe K-edge indicate that the local order around the Fe atom remains practically constant upon (Mn,Al) substitution. Measurements in the Mn K-edge show that distances Mn-Me suffer different changes with the increase in Mn substitution: a marked decrease in E and a slight decrease in E′, while DC remains constant. E and E′ values correspond to the distance between one Mn and one neighboring Me (Fe, Mn, Al) atom, both situated in two polyhedra linked by an edge. These polyhedra belong to the same double row of the goethite structure. DC value corresponds to the distance between one Mn and one Me (Fe, Mn, Al) atom, situated in two octahedral linked by one corner and belonging to two adjacent double chains. All the intermetallic distances are minor than the corresponding singly substituted goethites, this fact is attributed to the structure contraction due to the presence of Al(III) which restrains the axial distortion of Mn. Dissolution-time curves, resulting from exposure to 6 M HCl at 318 K, show that the dissolution rate slows with increasing Al substitution and consequent decrease of Mn substitution, and the shape of the curve becomes increasingly sigmoidal for mixed goethite with large Al content and Al-goethite. Dissolution kinetics of most samples are well described by the Kabai equation. Al dissolves almost congruently with respect to Fe, implying that it is homogeneously distributed in the structure. However, the convex χ_Mn:χ_Fe curve indicates that Mn tends to be concentrated in the outer layers of the goethite particles.     

Pedogenically degenerated illite and chlorite lattices aid to palaeoclimatic reconstruction for chronologically constrained(8-130 ka) loess-palaeosols of Dilpur Formation,Kashmir,India

Chronologically well-constrained loess-palaeosols(recorded glacial and inter-glacial climate) revealed pedogenesis induced ionic substitutions,caused end-member compositional deviations in illite and chlorite,linked to widespread climatic changes occurred during Late Pleistocene.Further,micro-level climatic resolution is yet to be resolved.Thus,layer-wise X-ray diffraction analyses of clay separates,followed by Rietveld refinement revealed varied cell parameters and interatomic distances.Obtained values for detrital and pedogenic illite and chlorite when plotted against stratigraphic succession show notable changes in the crystallographic axes.The illite lattices associated with inadequately pedogenized palaeosols have been altered into illite/smectite mixed layers,but,the chlorite lattices represent expansion of a-,b-and contraction of c-axes with much greater amount of distortions,suggestive of warm-humid and acidic environment.The detrital 48,44 and 83,74 bonded illite and chlorite with2 sub-types each,when pedogenized retained 48,44 and 34;and 83 and 74 bonds(in their neo-formed 3 and 2 sub-types),respectively.The Al-O bond shows expansion,but,unchanged Si-O and decreased Si-K and K-O bonds show loss of Al and retention of Si and K ions in the illite lattices.The illite with 32 atoms and 48 bonds represent contraction of K-O,Si-K,Al-O and Si-O bonds caused bond reinforcement;however,loss of Al~(3+)reflects all-out illite alteration.Owing to Al-O and K-O bond expansion,major K~+ and Al~(3+) ionic loss occurred during the LGM,however,further ionic loss depends upon the magnitude of the loess-palaeosol weathering that they have suffered.The clilate sensitive Fe,Mg and Al ionic losses for Fe-O,Mg-O and Al_(11)-O_9 bond length expansions were recognized in the chlorite lattices.Such ionic losses are common,but,complete distortion is attributed to Al,Si,Fe and Mg ionic losses,followed by weakening of Al-O,Si-O,Fe-O and Mg-O bonds.Though,Si-O_4 and Fe_1-O_4 bonds,and Si and Fe_(1 st) ions remain intact.Thus,three major glacial episodes of ～5 ka each occurred under alkaline environment,but,intervened by two successive cycles of 55 ka each,encompassing three alternate warm and cold climatic sub-cycles of 12-15 ka.But,the coldness increases with each warm-cold sub-cycle that attained the glacial maxima.Further,these events correlate well with the deep-sea records of the North Atlantic(MIS-1 to MIS-5 e) and CLP loess-palaeosols(～127 ka).     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.     

漳州地区白垩至纪I型和A型花岗岩中黑云母的矿物学特征

漳州地区白垩纪花岗岩由Ｉ型和Ａ型花岗岩组成，本文对该地区两类花岗岩中黑云母的矿物化学、矿物物理特征进行了系统研究。发现在两类花岗岩中的黑云母矿物学特征存在重大差别，如Ａ型花岗岩中黑云母更富铝、铁、氟及水而贫镁、硅，形成温度及氧逸度较低等。在Ａ型花岗岩中的黑云母穆斯堡尔谱也与Ｉ型不同，四极分裂（Ｑ．Ｓ）较高，且Ｆｅ￣（２＋）在Ｍ＿２位，Ｆｅ（３＋）在Ｔ位占位率也较高。两类花岗岩中的黑云母化学成分随岩浆演化也呈现不同的变化规律。黑云母的矿物学特征可提供花岗岩成因类型的有益信息。     

A Fe K-edge XAS study of amethyst

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.     

Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength (I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.     

黑云母的红外光谱研究

关于云母族矿物的红外光谱研究,国内外一些学者曾做过不少工作。笔者就近年来所收集到的一些产自宁芜地区、南岭地区花岗岩类岩石中27个黑云母样品,进行了红外光谱测定,确定了某些特征吸收峰的偏移及其与化学组分之间的关系,并探讨了黑云母矿物中主要金属阳离子的相互置换和     

Succession de subfacies métamorphiques en Vanoise méridionale (Savoie)

The Southern Vanoise is localized in the internal part of the Western Alps, in the Briançonnais zone. In Vanoise the following units can be distinguished (Fig. 1): a pre-hercynian basement (micaschists, glaucophanites, basic rocks), a permian cover (micaschists) and a mesozoic-paleocene cover (carbonate rocks). This area has been affected by the alpine metamorphic event characterized here by high and intermediate pressure facies. The rocks paragenesis are often unbalanced.The paleozoic rocks (Table 1) contain mainly: quartz, albite, paragonite, phengite, blue amphibole, chlorite, green biotite, garnet (Table 2). These minerals were analysed by an electron microprobe (Tables 3, 4 and 5). Mineral composition is highly variable: glaucophane is zoned (Table 5), white micas are more or less substituted with phengite (3.22O₃/FeO + MgO)<0.53] whereas the Al rich chlorites [(Al₂O₃/FeO + MgO)>0.6] are associated with the less substituted white micas (Si=3.2) (Tables 3 and 4). The phengites with a Si content 3.2 occur in rocks where the retromorphic evolution is the most pronounced and penetrative. A metamorphic evolution is characterized by the disappearance of glaucophane which corresponds to the appearance of Al rich chlorite and to the decrease of phengitic substitution.The samples analysis are plotted in the tetraedric diagram: K₂O-Al₂O₃-Na₂O, Al₂O₃-FeO, MgO, on which a special mathematical treatment was applied. This method calculates the location of rocks composition in the four minerals space. This location is internal when the per cent amounts of all four relevant minerals are positive, if any of them is negative, the point is external (Tables 6–9).In Southern Vanoise micaschists, 2 subfacies are successively present (Fig. 3):Subfacies I: glaucophane-chlorite-phengite (Si⁴⁺ 3.5)-paragonite. Then subfacies II: chlorite-albite-phengite (Si⁴⁺ 3.2)-paragonite.In basic rocks is found essentially: Subfacies III: glaucophane-garnet-phengite-paragonite or IV: glaucophane-garnet-phengite-albite. Then subfacies V: green biotite-chlorite-albite-paragonite.The assemblages I and II proceed through reaction: 2 glaucophane +1 paragonite+2 H₂O4.2 albite + 1 chlorite.The assemblage V appears with reactions: 1.8 glaucophane +2 phengite0.4 chlorite+2 green biotite + 3.6 albite +0.4 H₂O or 2 glaucophane +2 phengite +0.5 garnet+ 6 H₂O2 green biotite +1 chlorite+4 albiteThese reactions are controlled by hydratation: the composition variation of phengite and associated chlorite during the metamorphic evolution determines the stability of some minerals (particularly the glaucophane in Na₂O poor rocks).In same rocks the results of mathematical treatment is not consistent with the data (Tables 2, 6–9). This discrepancy corresponds to a desequilibrium between chlorite and phengite.These results imply a continuous metamorphic evolution between two stages (Fig. 6): a first stage (1) at 8 kb, 350 ° C; a second stage (2) at 2 to 3 kb, 400–450 ° C.     

Phase relations of biotite and stilpnomelane in the greenschist facies

Phase relations of biotite and stilpnomelane and associated silicate minerals have been studied in rocks of the greenschist facies, chiefly from Otago, New Zealand and western Vermont, but also from Scotland, Minnesota-Michigan iron range, and northwest Washington. That stilpnomelane in the greenschicht facies crystallizes initially with nearly all iron in the ferrous state is indicated by chemical analyses, high p-T experiments, and phase relationships. Alteration of stilpnomelane after metamorphism not only oxidizes iron but leaches potassium; corrections for both effects must be made in using analyses of brown stilpnomelane in studies of phase relations. Two discontinuous reactions which produce biotite at the biotite isograd have been identified:

1. muscovite+stilpnomelane+actinolite→ biotite+chlorite+epidote
2. chlorite+microcline→ biotite+muscovite. Biotite produced by the first of these reactions has a limited range of variation in Fe/Mg. As grade advances within the biotite zone more magnesian and ferruginous biotites become stable in consequence of the two continuous reactions:
3. muscovite+actinolite+chlorite→ biotite (Mg-rich)+epidote
4. muscovite+stilpnomelane→ biotite (Fe-rich)+chlorite.

Stilpnomelane is stable in muscovite-free rocks throughout the biotite zone, and even up to the grade at which hornblende becomes stable. Phengitic muscovite is stable throughout the biotite zone in New Zealand and thus apparently does not contribute to the formation of biotite until a higher grade is reached.     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.