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.     

Occurrence and breakdown of paragonite and margarite in the Greiner Schiefer Series (Zillerthal Alps,Tyrol)

Margarite and Paragonite are found coexisting in amphibolites of the Untere Schieferhülle in the area of the upper Schlegeistal (Zillerthal Alps, Northern Tyrol). These amphibolites are metamorphosed under conditions of the low grade amphibolite facies. The chemical composition of the two micas was determined by the electron microprobe. A maximum of 14 Mol-% margarite and 18 Mol-% muscovite enters into the paragonite, the margarite being entered by 20 to 50 Mol-% paragonite and a maximum of 10 Mol-% muscovite. There seems to be a solubility gap between margarite and paragonite in a range between 15 and 50 Mol-% margarite.At their margins the margarites and paragonites breakdown into a mixture of feldspar and into a fine, microscopically not identifiable phase. Plagioclases having An 28 to An 42 result from breakdown of paragonite, feldspars between An 50 and An 60 probably arose from breakdown of margarite. A definite statement on this probelem is not possible because the smallness and the inhomogeneity of the feldspar grains.Based on the experimental data concerning the stability of margarite, paragonite (±quartz, ±CO₂) and kyanite, the P-T-range of the metamorphosis is discussed.     

Mineralogy of New Caledonian metamorphic rocks

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 Si^iv 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.     

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     

Margarite in kyanite- and corundum-bearing anorthosite,amphibolite, and hornblendite from central Fiordland,New Zealand

Margarite is both abundant and widespread throughout a sequence of interstratified amphibolite, hornblendite, and metamorphosed anorthosite from the upper Lyvia River, central Fiordland. These rock types comprise part of a metamorphosed layered intrusion. Assemblages recorded from these rocks are the product of two distinct phases of metamorphism. First generation assemblages typically comprise plagioclase (An_84–96), hornblende, kyanite, and minor corundum. Clinozoisite and chlorite occur as late stage breakdown products of plagioclase and hornblende. Margarite developed during the second phase of metamorphism.Within the corundum-bearing rocks replacement of corundum or plagioclase by margarite can be observed directly. On the basis of these observations the following reaction is evident: 1 corundum+1 anorthite+1H₂O=1 margarite.In other assemblages the formation of margarite can be attributed to the breakdown of kyanite and clinozoisite according to the reaction: 2 kyanite+2 clinozoisite=1 margarite+3 anorthite.Margarite is found, however, to contain appreciable amounts of paragonite solid-solution (up to 28 mol%) and plagioclase produced (second generation) is not pure anorthite but of intermediate compositions (An_46–62). The reaction therefore involves the introduction of both soda and silica. Margarite also crystallized independently of clinozoisite according to a reaction of the general form: 5 pargasite+17 kyanite+19 H₂O =8 margarite+4 chlorite+7 plagioclase.Application of available experimental data suggests that the margarite formed between 550 and 720 ° C up to a maximum pressure of 9.5 kb. Whereas the involvement of albite component (second generation plagioclase) will tend to lower the temperatures and pressures necessary for the occurrence of margarite, this effect is partially offset by the significant amounts of paragonite end-member held within the margarite. An independent estimate of the metamorphic conditions in metapelites suggests that the introduction of albite lowers equilibration temperatures by about 2 ° C for every 1% albite.     

Distribution of elements between coexisting phengite and chlorite from the greenschist facies of the Tennant Creek area,Central Australia

The Lower Proterozoic Warramunga Group of the Tennant Creek area consists essentially of slates, phyllites and greywackes. ‘Porphyroidal’ rocks of pyroclastic origin, consisting of quartz porphyry and quartz-feldspar porphyry, form conformable horizons within the Warramunga Group and both show the same structural evolution. Recrystallization of phengite and chlorite in the Warramunga rocks was synchronous with regional folding and took place under greenschist facies conditions. Recrystallization of groundmass matrix into phengite and chlorite in the ‘porphyroidal’ rocks also took place under greenschist facies conditions during regional deformation. The major elements in coexisting phengite and chlorite from these groups were analysed in 14 samples by electron microprobe. Total analyses of 6 rocks were carried out by X-ray fluorescence spectrograph. Distribution of Mg and Fe²⁺ between coexisting phengite and chlorite shows a vague linear trend. The distribution coefficient K_D(Mg) is influenced in part by X_Mg of phengite. The tie lines for the mineral pairs on the triangular diagram show a subparallel trend. The Mg/Mg + Fe²⁺ of chlorite varies sympathetically with the Mg/Mg + Fe²⁺ of the rock.     

L'aspidolite fluorée : rôle des évaporites dans la genèse du rubis des marbres de Nangimali (Azad-Kashmir,Pakistan)

Ruby-bearing marbles from Nangimali, in the Azad-Kashmir, Pakistan, contain, besides phengite, different mica intergrowths: paragonite, phlogopite and aspidolite (sodium phlogopite). Both phlogopites, intimately linked and coexisting with paragonite, are fluorine rich, contrary to phengite and paragonite. F-enriched aspidolite is described for the first time. Phengite is either associated with phlogopite or could be isolated. The presence of aspidolite in the ruby-bearing marbles, together with other arguments such as salt solid inclusions and presence of anhydrite, suggest the implication of evaporites in the genesis of gem corundums. To cite this article: V. Garnier et al., C. R. Geoscience 336 (2004).     

Upper-pressure stability of synthetic margarite plus quartz

Thermodynamic calculations have shown that the dP/dT slope of the reaction 4 margarite+3 quartz5 kyanite +2 zoisite+3 H₂O as determined by Storre and Nitsch (1974) is too steep. This reaction has been reinvestigated using synthetic margarite, zoisite, kyanite, and natural quartz in the starting mixtures and using infrared spectroscopy to examine the run products. The experimentally determined dP/dT slope ranges between –2.2 and –17 bars/ K, which is in excellent agreement with predictions based on thermodynamics. An internally consistent set of univariant curves could be fitted to the experimental reversals for the above reaction and for the reactions margarite+ quartz anorthite+kyanite+H₂O and 2 zoisite+kyanite +quartz 4 anorthite+H₂O investigated by Nitsch et al. (1981) and Goldsmith (1981), respectively. Addition of up to 40 mol % of the component NaAl₂(Si₃Al) ·O₁₀(OH)₂ (paragonite) to margarite will increase the stability of the margarite solid solution plus quartz by 2–3 kbar without significantly affecting the dP/dT slope, making the paragenesis margarite plus quartz a good geobarometer.     

Chloritoid stability in manganese rich low-grade metamorphic rocks,Venn-Stavelot Massif,Ardennes

The Southern Venn-Stavelot Massif is characterized by Ordovician and Devonian rocks very rich in manganese and aluminum, which are attacked by a low grade regional metamorphism. The assemblages 1 (phengite, paragonite, chlorite, chloritoid, garnet, quartz, hematite, rutile) and 2 (phengite, paragonite, chlorite, kaolinite (andalusite, pyrophyllite), garnet, quartz, hematite, rutile) are of basic interest for the formation of chloritoid. As the two rock types are isofaciell and quasi-identical in chemistry except for the iron oxides, there is clear evidence for the influence of on the chloritoid formation at its lower p-T stability limit. This can be shown by a discussion of the phase relations of chloritoid, garnet, kaolinite, chlorite and phengite in respect to the oxidation ratio mol 2 Fe₂O₃x 100/2 Fe₂O₃+ FeO of the host rocks. Especially chloritoid and chlorite change their chemistry in a characteristic way with rising oxidation ratio in getting richer and richer in manganese and magnesium (chloritoid) and magnesium (chlorite). A simultaneous increase in trivalent iron in these phases is supposed. At an oxidation ratio of 85–90 the stability limit of chloritoid is reached. The increasing substitution of manganese and magnesium up to this limit should have a stabilizing effect. In a rough estimate the oxygen partial pressure is supposed to be in the order of 10⁻¹⁰ atm at the stability limit of chloritoid assuming a temperature of metamorphism between 360–400° C. Rocks with oxidation ratios between 90 and 100 are characterized by the presence of kaolinite. If the oxidation ratio is still higher (all iron as Fe³⁺, parts of the manganese in the trivalent state), the rocks belong to assemblage 3 (phengite, paragonite, chlorite, viridine, (kaolinite), (garnet), quartz, hematite, braunite, rutile). Dedicated to Prof. Dr. K. Jasmund at his 60. birthday.     

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.     

Petrology of the Strathgordon area,Western Tasmania: Si4+‐content of phengite mica as monitor of metamorphic grade

Important mineral assemblages of metapelite and quartzite of the Strathgordon area are phengite + chlorite + tourmaline + quartz and phengite + garnet + chlorite + tourmaline + quartz. Over a limited area the Si⁴⁺‐content of phengite does not vary significantly and is considered to depend only on the PT regime. The Si⁴⁺‐content of phengite coexisting with almandine‐grossular‐spessartine garnet and tourmaline indicate that the maximum metamorphism of the area occurred at 400 ± 50°C and 3 ± 1 kb.     

Separate or shared metamorphic histories of eclogites and surrounding rocks? An example from the Bohemian Massif

Eclogite boudins occur within an orthogneiss sheet enclosed in a Barrovian metapelite‐dominated volcano‐sedimentary sequence within the Velké Vrbno unit, NE Bohemian Massif. A metamorphic and lithological break defines the base of the eclogite‐bearing orthogneiss nappe, with a structurally lower sequence without eclogite exposed in a tectonic window. The typical assemblage of the structurally upper metapelites is garnet–staurolite–kyanite–biotite–plagioclase–muscovite–quartz–ilmenite ± rutile ± silli‐manite and prograde‐zoned garnet includes chloritoid–chlorite–paragonite–margarite, staurolite–chlorite–paragonite–margarite and kyanite–chlorite–rutile. In pseudosection modelling in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) using THERMOCALC, the prograde path crosses the discontinuous reaction chloritoid + margarite = chlorite + garnet + staurolite + paragonite (with muscovite + quartz + H₂O) at 9.5 kbar and 570 °C and the metamorphic peak is reached at 11 kbar and 640 °C. Decompression through about 7 kbar is indicated by sillimanite and biotite growing at the expense of garnet. In the tectonic window, the structurally lower metapelites (garnet–staurolite–biotite–muscovite–quartz ± plagioclase ± sillimanite ± kyanite) and amphibolites (garnet–amphibole–plagioclase ± epidote) indicate a metamorphic peak of 10 kbar at 620 °C and 11 kbar and 610–660 °C, respectively, that is consistent with the other metapelites. The eclogites are composed of garnet, omphacite relicts (jadeite = 33%) within plagioclase–clinopyroxene symplectites, epidote and late amphibole–plagioclase domains. Garnet commonly includes rutile–quartz–epidote ± clinopyroxene (jadeite = 43%) ± magnetite ± amphibole and its growth zoning is compatible in the pseudosection with burial under H₂O‐undersaturated conditions to 18 kbar and 680 °C. Plagioclase + amphibole replaces garnet within foliated boudin margins and results in the assemblage epidote–amphibole–plagioclase indicating that decompression occurred under decreasing temperature into garnet‐free epidote–amphibolite facies conditions. The prograde path of eclogites and metapelites up to the metamorphic peak cannot be shared, being along different geothermal gradients, of about 11 and 17 °C km^?1, respectively, to metamorphic pressure peaks that are 6–7 kbar apart. The eclogite–orthogneiss sheet docked with metapelites at about 11 kbar and 650 °C, and from this depth the exhumation of the pile is shared.     

Progressive Low-Grade Metamorphism of a Black Shale Formation, Central Swiss Alps, with Special Reference to Pyrophyllite and Margarite Bearing Assemblages

The unmetamorphosed equivalents of the regionally metamorphosedclays and marls that make up the Alpine Liassic black shaleformation consist of illite, irregular mixed-layer illite/montmorillonite,chlorite, kaolinite, quartz, calcite, and dolomite, with accessoryfeldspars and organic material. At higher grade, in the anchizonalslates, pyrophyllite is present and is thought to have formedat the expense of kaolinite; paragonite and a mixed-layer paragonite/muscovitepresumably formed from the mixed-layer illite/montmorillonite.Anchimetamorphic illite is poorer in Fe and Mg than at the diageneticstage, having lost these elements during the formation of chlorite.Detrital feldspar has disappeared. In epimetamorphic phyllites, chloritoid and margarite appearby the reactions pyrophyllite + chlorite = chloritoid + quartz+ H₂O and pyrophyllite + calcite ± paragonite = margarite+ quartz + H₂O + CO₂, respectively. At the epi-mesozone transition,paragonite and chloritoid seem to become incompatible in thepresence of carbonates and yield the following breakdown products:plagioclase, margarite, clinozoisite (and minor zoisite), andbiotite. The maximum distribution of margarite is at the epizone-mesozoneboundary; at higher metamorphic grade margarite is consumedby a continuous reaction producing plagioclase. Most of the observed assemblages in the anchi-and epizone canbe treated in the two subsystems MgO (or FeO)-Na₂O–CaO–Al₂O₃–(KAl₃O₅–SiO₂–H₂O–CO₂).Chemographic analyses show that the variance of assemblagesdecreases with increasing metamorphic grade. Physical conditions are estimated from calibrated mineral reactionsand other petrographic data. The composition of the fluid phasewas low in X_CO2 throughout the metamorphic profile, whereasX_CH4 was very high, particularly in the anchizone where a_H2Owas probably as low as 0.2. P-T conditions along the metamorphicprofile are 1–2 kb/200–300 °C in the anchizone(Glarus Alps), and 5 kb/500–550 °C at the epi-mesozonetransition (Lukmanier area). Calculated geothermal gradientsdecrease from 50 °C/km in the anchimetamorphic Glarus Alpsto 30 °C/km at the epi-mesozone transition of the Lukmanierarea.     

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.     

Compositions and phase relations of calcic amphiboles in epidote- and clinopyroxene-bearing rocks of the amphibolite and lower granulite facies,central Massachusetts,USA

Calcic amphiboles coexisting with epidotegroup minerals (zoisite, clinozoisite, epidote) and/or clinopyroxene±plagioclase±quartz±garnet occur in amphibolites and calc-silicate rocks that underwent amphibolite to lower granulite-facies metamorphism in the Acadian metamorphic high of central Massachusetts, USA. Across the region, peak metamorphic conditions range from about 580° C and 6.2 kbar to 730° C and 6.3 kbar. The coexistence of most Ca-amphiboles with Fe³⁺-rich epidote-group minerals suggests the presence of Fe³⁺ in most of these amphiboles. An empirical Fe³⁺ estimation for the microprobe analyses is based on two constraints: the Na?Ca content of the M4 sites of Ca-saturated, gravimetrically analyzed hornblendes gives the relation: Ca(M4) ^c =-1.479 Na(M4) ^c +2 (c=corrected). The second constraint is the stoichiometric equation Ca(M4)+Na(M4)+FM=15, where FM is the sum of all cations exclusive of Ca, Na, and K. Solving the two equations simultaneously gives: 20.185=0.479 Ca(M4)+1.479 ΣFM. Starting with the uncorrected values of Ca(M4) ^u and ΣFM(M4) ^u (u = uncorrected) of the all ferrous formula, the normalization factor NF for calculating the corrected cations of the ferric formulas is: 20.185/(0.478 Ca(M4) ^u +1.479 ΣFM ^u ). From the deficient oxygen the Fe³⁺ content which is equal to 2(23-ΣOX) can be calculated. Determinations of Fe³⁺ contents of four hornblende separates by Mössbauer spectroscopy are in agreement with the calculated values. The Ca-amphiboles show systematic changes in composition with increasing grade of metamorphism within the amphibolite and lower granulite-facies zones: increasing edenite and tschermakite substitution, increasing Ti content, and increasing Fe²⁺/(Fe²⁺+Mg) ratio. In addition, the coexisting clinopyroxenes are also characterized by an increase in Fe²⁺/(Fe²⁺+Mg) ratio. In quartz-free rocks with coexisting Ca-amphibole and plagioclase there is an increase in the ratio X _Ab/X _Ed, where X _Ab=Na/(Na+Ca) in plagioclase and X _Ed=Na in the amphibole A-site. These chemical changes in mineral composition together with the disappearance of epidote at the transition to granulite-facies metamorphic conditions are attributed to the continuous reaction: albite+epidote+Fe-Mg hornblende→Fe?Mg clinopyroxene+anorthite+(NaAlSi_-1)^Hbl+H₂O.     

Die Reaktion 2 Zoisit+1 CO2 ⇌ 3 Anorthit+1 Calcit+1 H2O

The equilibrium conditions of the following reaction 2 zoisite +1 CO₂?3 anorthite+1 calcite+1 H₂O 2 Ca₂Al₃[O/OH/SiO₄/Si₂O₇]+1 CO₂?3 CaAl₂Si₂O₈+1 CaCO₃+1 H₂O have been determined experimentally at total pressures of P _j= 2000 bars, P _f =5000 bars, and P _f =7000 bars. Owing to the vertical position of the equilibrium curves in isobaric T- \(X_{{\text{CO}}_{\text{2}} }\) diagrams, the composition of the binary H₂O-CO₂ fluid phase coexisting with zoisite is independent of temperature in the temperature interval investigated. According to our experiments, orthorhombic zoisite is only stable in equilibrium with a fluid phase at a concentration of CO₂ which is less than, respectively, ca. 2 Mol% CO₂ at P _f =2000 bars, ea. 6 Mol% at P _f =5000 bars, and ca. 10 Mol% at P _f =7000 bars. Thus, the fluid phase coexisting with zoisite is rich in H₂O. While this is independent of temperature the experimental data demonstrate that the influence of pressure cannot be neglected: With increasing pressure the concentration of CO₂ of the fluid phase coexisting with zoisite can rise a little. The position of the reaction studied, which is independent of temperature and exhibits small values of \(X_{{\text{CO}}_{\text{2}} }\) ,leads to two important petrogenetic conclusions:

1. The occurrence of zoisite is an indicator for a CO₂-poor and H₂O-rich fluid composition during metamorphism of marly calcsilicates.
2. If the concentration of CO₂ of the fluid phase coexisting with zoisite exceeds the equilibrium value of \(X_{{\text{CO}}_{\text{2}} }\) calcite+anorthite+H₂O is formed from zoisite+CO₂. Thus, a considerable increase in the anorthite-content of plagioelase is possible.

     

Preiswerkite and Na-(Mg,Fe)-margarite in eclogites

Preiswerkite and Na-(Mg,Fe)-margarite are two unusual micas very rare in Nature. They have been observed together in two eclogite occurrences (La Compointrie, France; Liset, Norway) as retrogression products in coronae or symplectites around kyanite. The chemical compositions and some physical properties of these micas are presented. The possible solid solutions and the conditions of stability are discussed. The preiswerkites display slight solid solution towards phengitic muscovite and Na-phlogopite. On the other hand, there is negligible solid solution towards more aluminous compositions; Al^IV ≤ 4 appears to be a composition limit for natural (K,Na)-micas. The margarites have an unusual Na-(Mg,Fe)-rich composition. They can be considered as a solid solution of about 2/3 mol% of margarite and 1/3 mol% of the theoretical end-member Na₂(Mg,Fe)₁Al^VI ₄[Si₄Al^IV ₄]O₂₀(OH)₄ (“Mica L”), with a possible substitution towards paragonite. The Marg_2/3 Mica L_1/3 composition (i.e. NaCa₂(Mg,Fe)_0.5 Al^VI ₆ [Si₆Al^IV ₆]O₃₀(OH)₆) might represent a particularly stable crystallographic configuration and could be considered as a true end-member. Many “sodian” margarites described in the literature are, in fact, complex solid solutions between margarite, paragonite and Marg_2/3 Mica L_1/3. The rarity of these micas is not related to extreme or unusual P-T conditions. They seem to be related to unusual chemical compositions, appearing in H₂O-saturated Na-Al-rich Si-poor systems, principally, if not only, at greenschist- or amphibolite-facies P-T conditions. Moreover, they are subject to crystallographic constraints whereby the high proportion of Al-tetrahedra create considerable distortion which prevents the entry of K into the interlayer site, thus necessitating Na (preiswerkite or ephesite) or Ca (margarite or clintonite) instead. Received: 21 April 1998 / Accepted: 25 January 1999     

Paragonite–hornblende assemblages and their petrological significance: an example from the Austroalpine Schneeberg Complex, Southern Tyrol, Italy

ABSTRACT Paragonite-bearing amphibolites occur interbedded with a garbenschist-micaschist sequence in the Austroalpine Schneeberg Complex, southern Tyrol. The mineral assemblage mainly comprises paragonite + Mg-hornblende/tschermakite + quartz + plagioclase + biotite + ankerite + Ti-phase + garnet ± muscovite. Equilibrium P–T conditions for this assemblage are 550–600°C and 8–10 kbar estimated from garnet–amphibole–plagioclase–ilmenite–rutile and Si contents of phengitic muscovites. In the vicinity of amphibole, paragonite is replaced by symplectitic chlorite + plagioclase + margarite +± biotite assemblages. Muscovite in the vicinity of amphibole reacts to form plagioclase + biotite + margarite symplectites. The reaction of white mica + hornblende is the result of decompression during uplift of the Schneeberg Complex. The breakdown of paragonite + hornblende is a water-consuming reaction and therefore it is controlled by the availability of fluid on the retrogressive P–T path. Paragonite + hornblende is a high-temperature equivalent of the common blueschist-assemblage paragonite + glaucophane in Ca-bearing systems and represents restricted P–T conditions just below omphacite stability in a mafic bulk system. While paragonite + glaucophane breakdown to chlorite + albite marks the blueschist/greenschist transition, the paragonite + hornblende breakdown observed in Schneeberg Complex rocks is indicative of a transition from epidote-amphibolite facies to greenschist facies conditions at a flatter P–T gradient of the metamorphic path compared to subduction-zone environments. Ar/Ar dating of paragonite yields an age of 84.5 ± 1 Ma, corroborating an Eoalpine high-pressure metamorphic event within the Austroalpine unit west of the Tauern Window. Eclogites that occur in the Ötztal Crystalline Basement south of the Schneeberg Complex are thought to be associated with this Eoalpine metamorphic event.     

Distribution of elements between coexisting phengite and chlorite from low grade rocks from Skiros Island,Greece

Summary The distribution of Fe²⁺ and Mg between coexisting phengite and chlorite has been examined in a suite of low-grade rocks. The distribution coefficientK _D(Mg) is influenced in part by the content of tetrahedral or octahedral Al of either chlorite or phengite and in part byX _Mg of phengite. The tie lines for the mineral pairs on a SAF triangular diagram show a subparallel trend.

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Elementarverteilung zwischen koexistierenden Phengit und Chlorit aus niedrig metamorphen Gesteinen von der Insel Skiros, Griechenland

Zusammenfassung Es wird untersucht, wie Fe²⁺ und Mg zwischen koexistierenden Phengit und Chlorit aus einer Folge schwach metamorpher Gesteine verteilt sind. Der VerteilungskoeffizientK _D(Mg) wird teils durch den Gehalt an tetraedrischem bzw. oktaedrischem Al in Chlorit oder in Phengit und teils durch dasX _Mg vom Phengit beeinflußt. Die Konoden zwischen den Mineralpaaren in einem SAF-Dreieckdiagramm zeigen subparallelen Verlauf.

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With 4 Figures     

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

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

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

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