Pressure dependence of structural parameters of paragonite

The compressibility and structure of a 2M₁ paragonite with composition [Na_0.88K_0.10Ca_0.01Ba_0.01] [Al_1.97Ti_0.007Fe_0.01Mn_0.002Mg_0.006]Si_3.01Al_0.99O₁₀OH₂ were determined at pressures between 1 bar and 41 kbar, by single crystal X-ray diffraction using a Merrill-Bassett diamond anvil cell. Compressibility turned out to be largely anisotropic, linear compressibility coefficients parallel to the unit cell edges being β_a=3.5(1)·10^?4, β_b=3.6(1)·10^?4, β_c=8.3(3)·10^?4 kbar^?1 (β_a:β_b·β_c=1:1028:2.371). The isothermal bulk modulus, calculated as the reciprocal of the mean compressibility of the cell volume, was 650(20) kbar. The main features of the deformation mechanism resulting from structural refinements at pressures of 0.5, 25.4, 40.5 kbar were: –?variation in sheet thickness, showing that compression of the c parameter was mainly due to the interlayer thickness reduction from 3.07 Å at 0.5 kbar to 2.81 Å at 40.5 kbar; –?the compressibility of octahedra was greater than that of tetrahedra, the dimensional misfit between tetrahedral and octahedral sheets increased with P, so that tetrahedral rotation angel α increased from 15° at 0.5 kbar to 21.6° at 40.5 kbar; –?the basal surface corrugation (Δz) of the tetrahedral layer, due to the different dimensions of M1 and M2 octahedra and to the octahedral distortion, decreased with P (Δz=0.19 and 0.12 Å at 0.5 and 40.5 kbar respectively). Comparison of the new data on paragonite with those of a K-muscovite and a Na-rich muscovite (Comodi and Zanazzi 1995) revealed a clear trend toward decreasing of compressibility when Na substitutes for K atoms in the interlayer sites.     

Application of a new approach to the calculation of electrostatic energies of expanded Di- and trioctahedral micas

The electrostatic lattice energies of expanded and unexpanded micas are calculated starting from a “generic” structure the ionic charges of which are varied. The mode of expansion is to move the layers apart perpendicular to (001), the K⁺ ions remaining midway between the layers. The energy required for expansion is a quadratic function of the layer charge. It is larger when the layer charge is in the octahedral sites (K _x Al_2?x Mg _x Si₄O₁₀(OH)₂) than when it is in the tetrahedral sites (K _x Mg₃Si_4?x Al _x O₁₀(OH)₂). Fluormicas have a slightly larger expansion energy than OH-micas. With the tetrahedral layer charge, dioctahedral micas have a slightly larger expansion energy than trioctahedral micas. This mode of expansion is less favourable than the mode usually adopted, viz. an expansion whereby the K ions divide themselves between the layers. The energy difference increases with the separation distance and is about 60 kJ mol^?1 at 2.5 Å expansion. An intercalated water layer would be necessary to stabilize the K ions in positions midway between the layers.     

An EMP and TEM--AEM Study of Margarite, Muscovite and Paragonite in Polymetamorphic Metabauxites of Naxos Cyclades, Greece) and the Implications of Fine-scale Mica Interlayering and Multiple Mica Generations

Coexisting white micas and plagioclase were studied by electronmicroprobe (EMP), and transmission and analytical electron microscopy(TEM—AEM) in greenschist- to amphibolite-grade metabauxitesfrom Naxos. The TEM—AEM studies indicate that sub-micronscale (0.01–1.0 µm thick) semicoherent intergrowthsof margarite, paragonite and muscovite are common up to loweramphibolite conditions. If unrecognized, such small-scale micainterlayering can easily lead to incorrect interpretation ofEMP data. Muscovite and paragonite in M₂ greenschist-grade Naxosrocks are mainly relics of an earlier high-pressure metamorphism(M₁). Owing to the medium-pressure M₂ event, margante occursin middle greenschist-grade metabauxites and gradually is replacedby plagioclase + corundum in amphibolite-grade metabauxites.The margarite displays minor ^IVAl_{3 VI}(Fe³⁺, Al) Si_-3 ^VI-_-1 andconsiderable (Na, K) SiCa_-1Al_-1 substitution, resulting in upto 44 mol% paragonite and 6 mol % muscovite in solution. Thecompositional variation of muscovite is mainly described by^VI(Fe²⁺, Mg) Si ^VI Al_-1^VI Al_-1 and _VI(Fe₃₊Al^-1) exchanges, thelatter becoming dominant at amphibolite grade, Muscovite issignificantly richer in Fe than margarite or paragonite. Ca—Na—Kpartitioning data indicate that margarite commonly has a significantlyhigher Na/(Na+ K+Ca) value than coexisting muscovite or plagioclase.Exceptions are found in several greenschist-grade rocks, inwhich M₁-formed mussovite may have failed to equilibrate withM₂ margarite. The sluggishness of K-rich micas to recrystallizeand adjust composidonally to changing P-T conditions is alsoreflected in the results of mus-covite-paragonite solvus thermometry.Chemical data for Ca—Na micas from this study and literaturedata indicate that naturally coexisting margarite—paragonitepairs display considerably less mutual solubility than suggestedby experimental work. The variable and irregular Na partitioningbetween margarite and muscovite as observed in many metamorphicrocks could largely be related to opposing effects of pressureon Na solubility in margarite and paragonite and/or non-equilibriumbetween micas. KEY WORDS: Ca—Na—K mica; margarite; metabauxite; Naxos; sub-micron-scale mica interlayering     

Characterization of non-equilibrium and equilibrium occurrences of paragonite/muscovite intergrowths in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy)

 Coexisting muscovite and paragonite have been observed in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy). The P-T conditions of this eclogite reached 570–650 °C and 19–21 kbar and the rocks show several stages of mineral growth during their retrograde path, ranging from the subsequent lower-P eclogite facies to the blueschist facies and then the greenschist facies. Muscovite and paragonite are very common in these rocks and show two texturally different occurrences indicating equilibrium and non-equilibrium states between them. In one mode of occurrence they coexist in equilibrium in the lower-P eclogite facies. In the same rock muscovite ± albite also replaced paragonite during a greenschist-facies overprint, as evidenced by unique across – (001) layer boundaries. The chemical compositions of the lower-P eclogite-facies micas plot astride the muscovite – paragonite solvus, whereas the compositions of the greenschist-facies micas lie outside the solvus and indicate disequilibrium. The TEM observations of the textural relations of the greenschist-facies micas imply structural coherency between paragonite and muscovite along the layers, but there is a sharp discontinuity in the composition of the octahedral and tetrahedral sheets across the phase boundary. We propose that muscovite formed through a dissolution and recrystallization process, since no gradual variations toward the muscovite – paragonite interfaces occur and no intermediate, homogeneous Na-K phase has been observed. Because a solid-state diffusion mechanism is highly unlikely at these low temperatures (300–500 °C), especially with respect to octahedral and tetrahedral sites, it is assumed that H₂O plays an important role in this process. The across-layer boundaries are inferred to be characteristic of such non-equilibrium replacement processes. The characterization of these intergrowths is crucial to avoiding erroneous assumptions regarding composition and therefore about the state of equilibrium between both micas, which in turn may lead to misinterpretations of thermometric results. Received: 3 February 1999 / Accepted: 19 October 1999     

Mössbauer effect and X-ray diffraction studies of synthetic iron bearing trioctahedral micas

Mössbauer effect, (ME) and powder X-ray diffraction, (XRD) have been used to study the relationship between cationic size, tetrahedral layer rotation, octahedral layer flattening, stability, and Mössbauer quadrupole splitting, qs, of iron bearing trioctahedral micas. Tetrahedral layer rotation accounts for much of the lattice adjustment but biotites that require an angle of rotation higher than 21 degrees are not stable. Both experimental and computational data show that qs for Fe³⁺ (IV) increases with increasing degree of tetrahedral layer rotation. A systematic increase of qs for Fe²⁺ (VI) is also observed, but this could be due to factors other than tetrahedral layer rotation.     

Evolution of 2:1 layered silicates in low-grade metamorphosed Liassic shales of Central Switzerland

White mica from the Liassic black shales and slates in Central Switzerland was analysed by transmission electron microscopy (TEM) and electron microprobe to determine its textural and compositional evolution during very low-grade prograde metamorphism. Samples were studied from the diagenetic zone, anchizone and epizone (T ≈100°–450 °C). Phyllosilicate minerals analysed include illite/smectite (I/S), phengite, muscovite, brammallite, paragonite, margarite and glauconite. Textural evolution primarily is towards larger, more defect-free grains with compositions that approach those of their respective end-members. The smectite-to-illite transformation reduced the amounts of the exchange components SiK_?1Al_?1, MgSiAl_?2, and Fe³⁺Al_?1. These trends continue to a lesser degree in the anchizone and epizone. Correlations between the proportion of smectite in I/S and the composition of I/S indicate that smectite layers may contain a high layer charge. Illite in I/S bears a compositional resemblance to macrocrystalline phengite in some samples, but is different in others. Paragonite first appears in the upper diagenetic zone or lower anchizone as an interlayer-deficient brammallite, and it may be mixed with muscovite on the nanometre scale. Owing to the small calculated structure factor for paragonite-muscovite superstructures, conventional X-ray powder diffraction cannot distinguish between mixed-layer structures and a homogeneous compositionally intermediate solid solutions. However, indirect TEM evidence shows that irregularly shaped domains of Na- and K-rich mica exist below 10 nm. Subsequent coarsening of domains at higher grades produced discrete paragonite grains at the margins of muscovite crystals or in laths parallel to the basal plane of the host muscovite. Margarite appears in the epizone and follows a textural evolution similar to paragonite in that mixtures of margarite, paragonite, and muscovite may initially occur on the nanometre scale. However, no evidence of interlayer-poor margarite has been found.     

A thermodynamic model for Fe–Mg dioctahedral K white micas using data from phase-equilibrium experiments and natural pelitic assemblages

The purpose of this study is to derive a solid-solution model for potassic white micas (KWM) encountered in rocks of various bulk compositions, over a wide range of P-T conditions. A compilation of phengite compositions lead us to propose a seven-thermodynamic-component (muscovite, Fe²⁺-Al-celadonite, Mg-Al-celadonite, annite, phlogopite, pyrophyllite and paragonite) ionic solid-solution model which accounts for the Tschermak, Fe-Mg, di/trioctahedral, pyrophyllitic and paragonitic substitutions observed in nature. A four-site mixing model with symmetric Margules parameters to model the Tschermak substitutions, asymmetric Margules parameters to model the other substitutions, and ideal intersite interaction has been adopted. In contrast to previous models, the relevant thermodynamic data and solid-solution properties are calibrated with independent sets of published experiments conducted for the KMASH, KFASH, KFMASH, and KNASH systems, as well as about 200 natural data involving KWM assemblages. The constraints span a wide range of pressure and temperature conditions (150 to 750 °C, 0.5 to 30 kbar), so that our model does not need to be extrapolated outside the calibration range to be used for P-T thermobarometric purposes. The calculated thermodynamic data are interconsistent with the TWQ thermodynamic database and solid-solution models, including that recently published for chlorites.     

Influence of structural factors on 29Si and 27Al NMR chemical shifts of phyllosilicates 2:1

The ²⁹Si and ²⁷Al nuclear magnetic resonance (NMR) analysis of synthetic trioctahedral phyllosilicates 2:1, with tetrahedral ratios Al _T/(Si + Al _T) ranging from 0 to 0.5, has shown that the ditrigonal distortion of tetrahedral rings (angle ) is the main factor controlling chemical shift values of tetrahedral components in both signals. The increase of ditrigonal rotation angle shifts these components towards more positive values. For each sample, the composition of tetrahedral and octahedral sheets determine the value of , and from this parameter, the mean tetrahedral Tot angle and the chemical shift values of components are deduced. For a given environment, variations on ditrigonal angle are responsibles for the observed evolution of chemical shift values with bulk composition. The comparative analysis of micas and saponite samples has demonstrated that the location of compensating charge (interlayer and octahedral sheet) does not affect chemical shift values.     

Paragenesis and chemical characteristics of the celsian−hyalophane−K-feldspar series and associated Ba-Cr micas in barite-bearing strata of the Mesoarchaean Ghattihosahalli Belt,Western Dharwar Craton,South India

The upper greenschist - lower amphibolite facies, argillaceous to chemical-exhalative metasedimentary sequence of the Mesoarchaean Ghattihosahalli Schist Belt (GHSB), southern India, has been examined with a special focus on the paragenesis and solid solution characteristics of barian feldspars and associated dioctahedral Ba-Cr-bearing micas. Barian feldspars occur as untwinned porphyroblasts in a recrystallized finely banded matrix of barite, quartz and minor white mica. Idioblastic celsian (Cls_98-76Or_2-20Ab_1-8) and hyalophane (Cls_55-39Or_35-51Ab₁₀) predate the greenschist-facies foliation, whereas xenoblastic hyalophane (Cls_44-35Or_45-59Ab_8–17) and mantles on celsian (Cls_45-35Or_42-60Ab_13-5) as well as xenoblastic barian K-feldspar (Cls₆Or₉₀Ab₂) postdate the last fabric-defining event. The preservation of extremely complex zoning patterns down to the micron-scale shows that diffusional homogenization did not operate at fluid-present low to medium-grade conditions (350–550 °C, 3–5 kb). Microstructures indicate that at these conditions barian feldspars deform exclusively by brittle fracturing and do not undergo recrystallization. Barian feldspar compositions confirm the positive correlation of Na-content with temperature and the existence of a narrow asymmetric compositional gap (Cls_90-85?Cls₅₅, ~350 °C) which probably closes at lower amphibolite facies conditions (X_c ~Cls_75; T_c ~550 °C). White micas are solid solutions of the end-members muscovite, ganterite (Ba_0.5?K_0.5)Al₂(Al_1.5Si_2.5)O₁₀(OH)₂, paragonite, celadonite with a significant substitution of ^[VI]Al by Cr. Zoning is a common feature with cores being enriched in Ba. The data document extensive Ba substitution for K from muscovite to ganterite, exclusively controlled by the coupled substitution ^[XII]K + ^[IV]Si ? ^[XII]Ba + ^[IV]Al and strongly dependent on bulk composition. The extent of solid solution from (Ms+Gnt) towards paragonite and celadonite end-members is controlled by the miscibility gap in the (Ms+Gnt)–Pg–Cel pseudoternary, with the Pg-substitution depending on temperature and the Cel-substitution on pressure. ^[IV]Si values between 3.1 and 3.3 in Ba-poor micas indicate minimum pressures of chemical equilibration in the order of 3–5 kbar, while the most sodian compositions of low-celadonite micas provide an upper temperature estimate of ~550 °C, consistent with P-T estimates for assemblages of metapelites (500–550 °C, 4–5 kb).     

Intermediate sodium–potassium mica in hydrothermally altered rocks of the Waterloo deposit,Australia: a combined SEM-EMP-XRD-TEM study

Metastable intermediate Na–K mica represents a product of hydrothermal alteration in volcanic rocks from the alteration halo of the Waterloo massive sulfide deposit, Australia. The XRD pattern of this solid solution between paragonite and muscovite is characterized by a rational series of basal reflections with d values intermediate between the end members. Transmission electron microscopy revealed that the intermediate Na–K mica forms thick stacks that belong to a two-layer polytype. Na-rich intermediate Na–K mica typically occurs together with paragonite whereas K-rich intermediate Na–K mica is intergrown with muscovite. The intermediate Na–K mica is interpreted to have formed as a result of the incomplete transformation of K-rich mica to Na-rich mica through dissolution and recrystallization processes driven by compositional changes of the hydrothermal fluids interacting with the volcanic rocks. Alteration must have proceeded under non-equilibrium conditions because the composition of the solid solution falls into the miscibility gap separating paragonite and muscovite.Editorial responsibility: T.L. Grove     

Ephesite,Na(LiAl2) [Al2Si2O10] (OH)2: II. Thermodynamic analysis of its stability and compatibility relations,and its geological occurrences

The trioctahedral mica ephesite, Na(LiAl₂) [Al₂Si₂O₁₀] (OH)₂, has a large -T stability field in the quaternary system NaAlSiO₄-LiAlSiO₄-Al₂O₃-H₂O. At temperatures below 400–500° C it coexists with diaspore, while at higher temperatures it occurs with corundum, until it decomposes to nepheline +eucryptite+corundum+H₂O at 600–800° C (Fig. 1). Nature faithfully reflects these phase relations; ephesite is found to coexist with diaspore or corundum in silicadeficient metamorphosed rocks or in hydrothermally altered nepheline-syenite pegmatite.Thermodynamic analysis of phase relations of ephesite in the silica saturated portion of the quinary system NaAlSiO₄-LiAlSiO₄-Al₂O₃-SiO₂-H₂O shows that the assemblage quartz+ephesite is always metastable with respect to paragonite+spodumene or paragonite+petalite at temperatures down to approximately 300° C (Fig. 3). At lower temperatures, a number of other phases like bikitaite, cookeite, Na-montmorillonite, and analcime are stabilized. Stability and compatibility relations involving these phases are presently not amenable to thermodynamic treatment due to lack of suitable data. Nevertheless, the absence of the assemblage quartz+ephesite in nature seems to vindicate our conclusion that it is metastable down to at least 300° C.The frequently encountered assemblage quartzspodumene (or petalite)-microcline-albite of some lithium pegmatites contains muscovite (±lepidolite), rather than paragonite. The absence of paragonite in such rocks is best explained by the inherent metastability of the phase-pair paragonite+microcline with respect to muscovite+albite. The pegmatite bulk compositions plot in the four-phase field spodumene (petalite)-microcline-muscovite-albite, cutting out paragonite from the observed assemblage Thus, absence of paragonite-spodumene or paragonitepetalite in nature reflects lack of suitable bulk compositions in rocks.     

Calculation of muscovite-paragonite-alkali feldspar phase relations

Experimental data on K-Na exchange between NaCl-KCl-H₂O fluids and alkali feldspars or white micas, and end-member dehydration reactions of white mica (± quartz to alkali feldspar plus corundum (or Al₂SiO₅) and H₂O have been used to evaluate K-Na exchange potentials between coexisting white mica and alkali feldspar. Calculations using these exchange potentials and Margules parameters for excess molar Gibbs energies of alkali feld-spars and white micas have permitted the construction of a projected binary phase diagram for the white mica dehydration. Extrapolation to higher temperatures and pressures gives a topology wholly consistent with field evidence. The subsolidus univariant curves intersect H₂O-saturated minimum-melting curves. At pressures greater than about 6 kbar the common assemblage Ms+Or+Ab+Q could undergo H₂O-saturated minimum-melting at lower temperatures than the disappearance of paragonite or the kyanite-sillimanite isograd in more aluminous rocks. The apparent restriction of anatexis to rocks above the second sillimanite isograd may imply that activity of H₂O is usually less than unity in high-grade regional metamorphism.     

Pressure-induced phase transition in synthetic trioctahedral Rb-mica

 The crystal structure of a synthetic Rb analog of tetra-ferri-annite (Rb–TFA) 1M with the composition Rb_0.99Fe²⁺ _3.03(Fe³⁺ _1.04 Si_2.96)O_10.0(OH)_2.0 was determined by the single-crystal X-ray diffraction method. The structure is homooctahedral (space group C2/m) with M1 and M2 occupied by divalent iron. Its unit cell is larger than that of the common potassium trioctahedral mica, and similar lateral dimensions of the tetrahedral and octahedral sheets allow a small tetrahedral rotation angle α=2.23(6)°. Structure refinements at 0.0001, 1.76, 2.81, 4.75, and 7.2 GPa indicate that in some respects the Rb–TFA behaves like all other micas when pressure increases: the octahedra are more compressible than the tetrahedra and the interlayer is four times more compressible than the 2:1 layer. However, there is a peculiar behavior of the tetrahedral rotation angle α: at lower pressures (0.0001, 1.76, 2.81 GPa), it has positive values that increase with pressure [from 2.23(6)° to 6.3(4)°] as in other micas, but negative values −7.5(5)° and −8.5(9)° appear at higher pressures, 4.75 and 7.2 GPa, respectively. This structural evidence, together with electrostatic energy calculations, shows that Rb–TFA has a Franzini A-type 2:1 layer up to at least 2.81 GPa that at higher pressure yields to a Franzini B-type layer, as shown by the refinements at 4.75 and 7.2 GPa. The inversion of the α angle is interpreted as a consequence of an isosymmetric displacive phase transition from A-type to B-type structure between 2.81 and 4.75 GPa. The compressibility of the Rb–TFA was also investigated by single-crystal X-ray diffraction up to a maximum pressure of 10 GPa. The lattice parameters reveal a sharp discontinuity between 3.36 and 3.84 GPa, which was associated with the phase transition from Franzini-A to Franzini-B structure. Received: 21 October 2002 / Accepted: 25 February 2003     

Chemistry of micas from kimberlites and xenoliths—I. Micaceous kimberlites

Micaceous kimberlites from South Africa and Canada contain two types of groundmass mica less than 1 mm across. Very rare Type I micas are relatively iron-rich with $\text{mg [ = Mg/(Mg + Fe)] 0.45–0.65}$, TiO₂ 3–6 wt%, Al₂O₃ 14–16wt%, no Fe³⁺ required in tetrahedral sites, low NiO (~0.02 wt%), and relatively high na [Na₂O/(Na₂O + K₂O)] 0.02–0.03. The much more abundant Type II micas are variable in composition, but relative to Type I micas are more magnesium (mg 0.80-0.93), lower in TiO₂ (0.7–4.0 wt%) and Al₂O₃ (6.8–14.2 wt%), have substantial Fe³⁺ in tetrahedral sites, and have relatively low na. Both types may have rims with compositions indicative of mica-‘serpentine’ mixtures resulting from reaction with a highly aqueous fluid. The petrographically-determined ‘serpentine’ is chemically of two types: Fe-rich serpentine and Fe-rich talc. Associated phases in the ground-mass vary from one kimberlite to another: calcite, dolomite, diopside, chromite, Mg-ilmenite, perovskite, barite, pyrite, pentlandite, millerite?, heazlewoodite?, quartz.Inter-grain variations in composition of Type II micas may result from establishment of local reservoirs on a mm scale, consequent upon mechanical mixing and competition of other phases for minor elements (e.g. chromite for Cr, serpentine for Ni).Type I micas may result from an intrusive precursor (carbonatitic?) to kimberlite, perhaps genetically related, which was incorporated into a later pulse of kimberlite from which the Type II micas crystallized.     

On the “late” formation of paragonite and its breakdown in pelitic rocks of the southern Damara Orogen (Namibia)

The formation of paragonite at the transition from the low-grade to the medium-grade matamorphism and its breakdown in the presence of quartz in the upper medium grade in common metapelites is investigated.The microprobe work on the white micas from the low and medium-grade rocks yields compositional differences in respect to the celadonite substitutions and the paragonite content. The low-grade white micas are phengites having Si^[4] 6.25 to 6.44 and Al_tot 4.89 to 5.20. The paragonite component in solid solution in the phengites ranges from 11 to 17 mole %. In the transition from the low-grade to the medium-grade metamorphism, concomitant with the breakdown of chlorite, the phengites change to muscovites having Si^[4] 6.07 to 6.16 and Al_tot 5.36 to 5.56. At the same time, the amount of paragonite in solid solution increases up to 22±2 mole % and paragonite makes its first appearance as a separate mineral. The increase of the percentage of paragonite in solid solution in the muscovites is due to the drastical modal decrease of muscovite in the course of the breakdown of chlorite. The formation of paragonite is readily explained by the muscovite-paragonite solvus. Paragonite forms thin lamellae (1–20 m) interlayered with muscovite lamellae (1–40 m). The average composition is Pg_88.5Ms₇Mar_4.5. Paragonite occurs together with staurolite+biotite, kyanite+biotite, cordierite +biotite, and andalusite+biotite. In the presence of quartz, it breaks down in the lower part of the andalusite zone to andalusite and albite-rich plagioclase. At the same time, the amount of paragonite in solid solution in the muscovites decrease to 11–15 mole %. The basal spacings d(002) of the phengites and muscovites investigated show a clear dependence on the Na⁺ content and the celadonite substitutions.     

Mössbauer studies of synthetic and natural micas on the polylithionite-siderophyllite join

Mössbauer studies of micas on the polylithionite-side-rophyllite join show the existence of a relation between the quadrupole splitting (ΔE _Q) values of Fe²⁺ high spin doublets and both cationic and anionic composition of micas. This linear relation is positive as Li₂O content increases and negative as F content increases. In the lithium iron micas, the inner ferrous quadrupole doublet is assigned to the cis-site M(2), while the outer doublet is assigned to the trans-site M(1). A random distribution of Fe²⁺ is observed in fluorine-rich compositions, while slight enrichment of the M(1) site is noticed in hydroxyl compositions, perhaps due to a more sensitive oxidation in situ in M(2) than M(1) sites. The Mössbauer spectrum of siderophyllite K₂(Fe ₄ ²⁺ Al₂)(Si₄Al₄)O₂₀(OH)₄ shows the presence of only one ferrous doublet, which is assigned to M(2) sites. Hence from Mössbauer data we must consider a clintonite (“xanthophyllite”) structure for this mica. The ordered octahedral layer has two distorted ferrous cis-sites and one, more symmetrical, aluminum trans-site.     

Fe-Li云母化学成分的解释和分类

用置换矢量概念解释了115个天然 Fe-Li 云母化学成分的变化。Fe-Li 云母是三八面体 Li-Fe-Al 云母,其基本置换是四锂云母置换。由于 Al-Li 白云母置换和白云母置换的影响,其化学组成变化的基本趋势呈明显的非线性,因而 Fe-Li 云母不是真正的二元系。作为 Fe-Li 云母,富铁黑云母和铁叶云母都是最富铁的成员,因而建议称 Fe-Li 云母为黑云母-锂云母系列。根据化学成分,晶胞参数和折光率的异常变化还提出了该系列自然分类的方案。     

Coexisting phengite,paragonite and margarite in metasediments of the mittlere Hohe Tauern,Austria

The assemblages phengite-paragonite, phengite-margarite and phengite-paragonitemargarite are very common in metasediments of a N-S profile in the middle sector of the Hohe Tauern. The Si⁴⁺-content of phengite shows no regular change with increasing temperature from north to south along the profile. The variations in the d ₀₀₂ basal spacings of phengite coexisting with paragonite are not only dependent on the Na⁺ content of phengite but also on the Mg²⁺+Fe²⁺ content of the micas. Neither the sodium content in phengite nor the potassium content in paragonite shows any dependence on temperature. Chemical analyses of coexisting phengite, paragonite and margarite give the extent of the three-phase-region which is characterized by a small amount of margarite in paragonite (4 Mol%), by a large quantity of Na⁺ in margarite (28 Mol% paragonite), and limited miscibility between phengite and paragonite.     

Isothermal compression of low-cordierite to 30 kbar (25° C)

The compression of cordierite (Mg, Fe)₂Al₄Si₅O₁₈·n (H₂O, CO₂; Na⁺, K⁺) has been studied up to 30 kbar (25° C) by volumetric measurements with a piston cylinder apparatus and by X-ray measurements with a diamond-anvil cell. Natural cordierite of intermediate Mg-Fe composition and synthetic Mg-cordierite served as samples. Two discontinuities at 2.2±0.3 and 9.0±0.6 kbar which are correlated with very small volume changes (0.3?0.05%) have been found. The X-ray data indicate, however, no symmetry change of the crystal structure. The two discontinuities are interpreted as phase transitions. The two discontinuities establish three pressure dependent phases referred to as low-pressure (LP)-, first high-pressure (HP1)- and second high-pressure (HP2)-phase. The gross compressibility of cordierite decreases from 1.1 Mbar^?1 at low pressure to 0.7 Mbar^?1 at 30 kbar for the intermediate Mg-Fe cordierite, and to 0.4 Mbar^?1 for Mg-cordierite. Depending on the pressure transmitting medium used in the two different compression techniques, two kinds of compression behavior are observed for cordierite. The measurements with the piston cylinder apparatus where lead is used as quasihydrostatic pressure medium indicate normal compression properties. The X-ray data, however, obtained with the diamond anvil cell where a methanol-ethanol mixture provides hydrostatic pressure conditions yield, e.g. for the HP1-phase a dramatic decrease in compressibility to almost zero. IR-spectra from samples of augmenting experiments with methanol, deuteromethanol and D₂O as pressure media indicate that pressure media of which the molecule size is comparable with the dimensions of the cordierite channels may be incorporated in the structure. This suggests that under such hydrostatic conditions the compression of cordierite is modified by a structure internal component which is acting via the channel system.     

Variation in sericite compositions from fracture zones within the Coso Hot Springs geothermal system

Two types of white micas are found in drillhole samples within the geothermal system at Coso Hot Springs. Low-permeability zones of the crystalline basement contain coarse-grained relict muscovite, whereas rock alteration near fracture zones at temperatures > 150°C is characterized by abundant finegrained sericite in association with secondary calcite and quartz and unaltered relict microcline. In this hydrothermal sericite there is an increase in interlayer K, octahedral Mg + Fe_total and tetrahedral Al with increasing temperature between ~215° to >250°C.Thermodynamic activity of the Al₂Si₄O₁₀(OH)₂ component of serielles, calculated using site-mixing approximations of Helgeson and Aagaard (1985), decreases with increasing temperature between ~215° and >250°C. As a consequence of the observed variations in the interlayer, octahedral and tetrahedral site occupancies, the activity of KAl₂(AlSi₃O₁₀(OH)₂ is essentially constant in the Coso seriates over this temperature range. The calculated equilibrium distribution of aqueous species in the hydrothermal solutions produced from well 16−8, together with cation-activity phase diagrams that account for variations in sericite composition, requires a pH of ~6.7–6.8 at temperatures between 236° and 250°C. Comparison of predicted and observed phase relations with fluid compositions indicate that seriates are in local equilibrium with the geothermal reservoir fluid, whereas relict metamorphic muscovites are metastable.Although the compositions of hydrothermal sericites are a complex function of temperature, pressure and geothermal fluid composition, compositional relations observed at Coso together with published compositions of hydrothermal dioctahedral layer-silicates from the Salton Sea geothermal system demonstrates that elemental compositions of interlayer K and tetrahedral Al increase systematically with increasing temperature despite the dramatic differences in fluid compositions between these two geothermal systems. This suggests that the observed variations in interlayer and tetrahedral site occupancy is largely dependent on the enthalpy of hydrolysis reactions representing equilibrium between sericite solid solutions and the geothermal reservoir fluids.