A Petrogenetic Grid for Reactions Producing Biotite and other Al-Fe-Mg Silicates in the Greenschist Facies

This report presents an analysis of phase relations among biotite,muscovite, chlorite, stilpnomelane, actinolite and K-feldsparin a ten component system within the greenschist facies. Itis based on study of the chemical composition of these minerals,on calculations to balance chemical equations-among them, andon their field distribution. A petrogenetic grid resulting fromthis treatment consists of a single invariant point and multipleunivariant lines, the number depending on what part of the assemblageset is held constant. The reactions which involve biotite aresimilar to previously proposed reactions for the biotite isograd.At high pressure, biotite is produced from muscovite+stilpnomelane+actinolite?K-feldspar.At low pressure, chlorite+K-feldspar?stilpnomelane?actinolitereact to form biotite. A biotite-free reaction, not previouslyidentified, divides the chlorite zone into high pressure andlow pressure fields, characterized by the assemblages muscovite+stilpnomelane+actinoliteand chlorite+K-feldspar, respectively. In the blueschist facies,muscovite plus stilpnomelane and/or actinolite are stable insteadof biotite.     

A Petrogenetic Grid for Reactions Producing Biotite and other Al--Fe--Mg Silicates in the Greenschist Facies

This report presents an analysis of phase relations among biotite,muscovite, chlorite, stilpnomelane, actinolite and K-feldsparin a ten component system within the greenschist facies. Itis based on study of the chemical composition of these minerals,on calculations to balance chemical equationsamong them, andon their field distribution. A petrogenetic grid resulting fromthis treatment consists of a single invariant point and multipleunivariant lines, the number depending on what part of the assemblageset is held constant. The reactions which involve biotite aresimilar to previously proposed reactions for the biotite isograd.At high pressure, biotite is produced from muscovite+stilpnomelane+actinolite±K-feldspar.At low pressure, chlorite+K-feldspar±stilpnomelane±actinolitereact to form biotite. A biotite-free reaction, not previouslyidentified, divides the chlorite zone into high pressure andlow pressure fields, characterized by the assemblages muscovite+stilpnomelane+actinoliteand chlorite+K-feldspar, respectively. In the blueschist facies,muscovite plus stilpnomelane and/or actinolite are stable insteadof biotite.     

The structure of the Moine and Dalradian Rocks in the Dalmally District of Argyllshire,Scotland

Two phases of deformation are described from the area. D1 is related to the first phase movements widely recognised in the Dalradian; D2 is related to more localised modifications of the D1 fold pattern. Four major D2 folds are recognised from the evidence of minor structures. Three of these, the Beinn Chuirn, the Ben Lui and the Ra Chreag Folds, had previously been considered as D1 structures, whilst the fourth, the Dalmally Fold, was unrecognised. These folds provide continuity between the southeast facing of the D1 folds of the Moine and Ballachulish Succession of Glen Orchy (Thomas and Treagus 1968) and the southeast facing of the D1 Jay Nappe (Shacketon 1958) in the Iltay Succession above. The D2 deformation reaches a climax at the junction between the two Successions, the Iltay Boundary Slide, which is now regarded as a D2 structure. The regional implications of these results are briefly considered.     

Lithological and Structural Controls on Regional 3-D Fluid Flow Patterns during Greenschist Facies Metamorphism of the Dalradian of the SW Scottish Highlands

Greenschist facies metabasite sills enclosed within phyllitesand psammites of the Dalradian Supergroup of the SW ScottishHighlands have been used as quantitative sensors of fluid flow,from which ‘fossil’ fluid flow-paths have been mapped.Infiltration of H₂O–CO₂ fluid caused carbonation of themetabasite assemblage. Consequently, metabasite sills have developeda characteristic asymmetric zonation of reacted (carbonate-bearing)margins and unreacted (carbonate-absent) interiors. Reactionfront advection theory has been used to constrain the time-integratedfluid flux and flow direction in one dimension, for each sill,from the widths of the reacted margins. Three-dimensional fluxesand flow directions have been constrained from one-dimensionalfluxes by geometrical computation, and regional fluid flow patternshave been deduced. On a regional scale, fluid flow was channelled through phyllitesand focused towards the axial zone of major antiformal foldstructures. Fluid flow was channelled through the 6 km thickArdrishaig Phyllites, within which fluid fluxes were found toincrease exponentially with proximity to the axial surface ofthe Ardrishaig Anticline. Fluid flow through the psammites waslimited to narrow zones of intense deformation associated withmetabasic or phyllitic intercalations. Although time-integratedfluid fluxes were locally high (4 10² m³/m²), average fluxes(100 m¹/m²) are compatible with availability of fluid from underlyingdevolatilizing rocks. Complete isotopic homogenization of phyllites,psammites and metabasites within the axial region of the ArdrishaigAnticline is predicted by these high measured fluxes. KEY WORDS: 3-D flow; Dalradian; SW Scotland; greenschist facies; metabasites ^*Corresponding author. Telephone: 0131-650-5885 Fax: 0131-668-3184 E-mail: askelton{at}glg.ed.ac.uk     

变质火山岩、火山碎屑岩的绿片岩相成岩格子和成岩格子的若干特征

变质火山岩、火山碎屑岩的绿片岩相成岩格子可用阳起石—黑云母—方解石—绿泥石—绿帘石—白云母六相三元系和钠长石—阳起石—黑云母—方解石—绿泥石—绿帘石六相三元系成岩格子来表示,石英往往为过剩组分。在只讨论两个强度相同的变量前提下,每个六相三元系的成岩格子都只可能有一对成对的成岩格子,且这对成岩格子的非封闭双变区的分区相同、分区之间的边界斜率相同、相应的单变线的排列顺序也相同,因此,六相三元系的每个成岩格子中的不变点数、单变线数、和双变区数之间的关系可用数学式来表示。     

Staurolite-forming reactions in the eastern Dalradian rocks of Scotland

Data on mineral and rock compositions along with textural relations are used to deduce the staurolite-forming reactions in eastern Dalradian rocks in Scotland. Initially staurolite is formed as a product of the breakdown of the assemblage chloritoid +quartz in iron-rich metapelites. With increase in grade the iron-rich rocks are succeeded by more magnesium-rich ones and staurolite is formed as a product of the breakdown of the assemblage chloritoid +chlorite+muscovite.     

The Graphical Analysis of Greenschist to Amphibolite Facies Mineral Assemblages in Metabasites

The mineral assemblages of greenschist to amphibolite faciesmetabasites may usually be represented in a system of principalcomponents: CaO-Al₂O₃-(Fe₂O₃)-FeO-MgO-Na₂O-SiO₂-C0₂-H₂O Assemblages co-existing with quartz, ‘albite’, ‘epidote’and a fluid of restricted composition, may be shown by projectionin a CAFM subsystem from ‘epidote’ onto an extendedAFM plane. This projection is analogous to the Thompson projectionfor pelites and is particularly useful in displaying the effectsof Fe/Mg and Al substitution in the silicates as well as incorporatingCaO; it is illustrated by plotting assemblages from the SouthernAlps of New Zealand and the Scottish Highlands and demonstrateschanges occurring with grade in the assemblages. Some commonisograds and facies boundaries are seen to be strongly dependenton bulk rock composition. In some cases MnO must be consideredas an additional component. A model of P_solid=P_fluid, where the fluid is composed of CO₂+H₂Ois consistent with many greenschist to amphibolite facies metabasicassemblages. Natural assemblages indicate this fluid phase tohave restricted mobility. Theoretical consideration of mineralreactions resulting from increasing X_CO2 in conjunction withdata from natural mineral assemblages, leads to the distinctionof five principal types of assemblage which may be expectedas a function of varying X_CO2. Recognition of these assemblagetypes provides a useful guide to relative X_CO2 during metamorphism.     

The Graphical Analysis of Greenschist to Amphibolite Facies Mineral Assemblages in Metabasites

The mineral assemblages of greenschist to amphibolite faciesmetabasites may usually be represented in a system of principalcomponents: CaO–Al₂O₃–(Fe₂O₃)–FeO–MgO–Na₂O–SiO₂–CO₂–H₂O Assemblages co-existing with quartz, ‘albite’, ‘epidote’and a fluid of restricted composition, may be shown by projectionin a CAFM subsystem from ‘epidote’ onto an extendedAFM plane. This projection is analogous to the Thompson projectionfor pelites and is particularly useful in displaying the effectsof Fe/Mg and Al substitution in the silicates as well as incorporatingCaO; it is illustrated by plotting assemblages from the SouthernAlps of New Zealand and the Scottish Highlands and demonstrateschanges occurring with grade in the assemblages. Some commonisograds and facies boundaries are seen to be strongly dependenton bulk rock composition. In some cases MnO must be consideredas an additional component. A model of P_solids=P_fluid, where the fluid is composed of CO₂+H₂Ois consistent with many greenschist to amphibolite facies metabasicassemblages. Natural assemblages indicate this fluid phase tohave restricted mobility. Theoretical consideration of mineralreactions resulting from increasing X_co2, in conjunction withdata from natural mineral assemblages, leads to the distinctionof five principal types of assemblage which may be expectedas a function of varying X_Co2. Recognition of these assemblagetypes provides a useful guide to relative X_Co2 during metamorphism. ^* Present Address: Department of Geology, University of California, 405 Hilgard Avenue, Los Angeles, California 90024.     

The boyndie syncline,a D1 structure in the Dalradian of Scotland

The structure of the Dalradian rocks of the Banffshire coast has been re-examined. It is shown that D₁ structures face upwards along the entire section and the major Boyndie Syncline (Sutton and Watson 1956) must also be of D₁, age and not D₃ as proposed by Johnson (1962). D₂ structures are developed in the west, most strongly in the Portsoy Group and Cowhythe Gneiss where they may be related to the Portsoy Thrust (Elles 1931). East of the Cowhythe Gneiss D₂ structures are not developed but D₃ structures are of local importance. Porphyroblast growth is considered to be post-D₁, pre-D₃ related to the ‘active’ D₂ deformation in the west (Barrovian) and to the ‘static’ D₂ interval in the east (Buchan). The wider implications of these conclusions for Dalradian structure are briefly considered.     

Thorium and uranium in some pelitic rocks from the Dalradian,Scotland

Instrumental neutron-activation analysis for the determination of Th and U in rocks is superior to the delayed-neutron method when a low-power reactor is used. Results using these methods on pelitic rocks from the Dalradian of Scotland indicate Th values higher and U values lower than sediments from elsewhere. There is no evidence of Th or U movement during metamorphism and the areal variations found are due to the different provenance of the rocks.     

Models for the tectonothermal evolution of the eastern Dalradian of Scotland

Abstract The preserved array of pressures in the eastern Dalradian indicates that considerable syn- to post-metamorphic differential uplift has occurred. This inferred differential uplift suggests that Buchan sillimanite zone rocks originally lay at higher structural levels than presently adjacent cooler kyanite zone rocks to the west. A number of features are believed to coincide with the western margin of the sillimanite zone. These are a maximum in temperature, sharp thermal features, a high strain zone, and a train of metabasites. These features are explained by invoking syn-metamorphic movement between the Buchan sillimanite zone and the kyanite zone to its west, involving some horizontal component of movement. It is suggested that the lateral, now eroded, equivalents of the Buchan area once provided part of the required tectonic thickening for other parts of the Dalradian. Areas surrounding the Buchan area suffered tectonic burial followed by metamorphism during uplift relative to the Buchan area.     

Comparison of strain and magnetic fabrics in Dalradian rocks from the southwest Highlands of Scotland

The magnetic fabrics of 235 samples from 31 localities in Argyllshire, Scotland were determined to study the development of the Caledonian tectonic fabric in the southwest Highlands of Scotland. The regional fabric indicates a strong NE-SW compressional foliation due to the primary deformational phases, which in parts has been overprinted by secondary deformations. A detailed comparison of the anisotropy data and the available strain data shows that the two fabric ellipsoids are co-axial, and that their axial mean ratios seem to be related by an empirical power relationship of the type:

$\text{Xi}\text{Xj}\text{=}\text{li}\text{lj}{}^{\mathrm{a}}$

(for i = 1,2,3; j = 1,2,3 and i ≠ j) where χ_i and χ_j are orthogonal principal axes and l_i and l_j are the corresponding orthogonal principal strain axes. The exponent a for the sites from Scotland is 0.088 ± 0.017 compared with 0.142 ± 0.001 and 0.145 ± 0.005 found in the Caledonian slates of the English Lake District and the Welsh slate belt.     

Chromite in Komatiites, II. Modification during Greenschist to Mid-Amphibolite Facies Metamorphism

Chromite compositions in komatiites are influenced by metamorphicprocesses, particularly above 500°C. Metamorphosed chromiteis substantially more iron rich than igneous precursors, asa result of Mg–Fe exchange with silicates and carbonates.Chromite metamorphosed to amphibolite facies is enriched inZn and Fe, and depleted in Ni, relative to lower metamorphicgrades. Relative proportions of the trivalent ions Cr³⁺, Al³⁺and Fe³⁺ are not greatly modified by metamorphism up to loweramphibolite facies, although minor Fe³⁺ depletion occurs duringtalc–carbonate alteration at low temperature. SignificantAl is lost from chromite cores above 550°C, as a resultof equilibration with fluids in equilibrium with chlorite. ElevatedZn content in chromite is restricted to rocks with low (metamorphic)Mg/Fe ratios, and is the result of introduction of Zn duringlow-temperature alteration, with further concentration and homogenizationduring prograde metamorphism. Cobalt and Mn also behave similarly,except where carbonate minerals are predominant in the metamorphicassemblage. Chromite at amphibolite facies is typically extensivelyreplaced by magnetite. This is the result of incomplete metamorphicreaction between chromite and chlorite-bearing silicate assemblages.Magnetite compositions at the inner chromite–magnetiteboundary are indicators of metamorphic grade. KEY WORDS: chromite; komatiite; spinel; metamorphism; Zn     

Regional metamorphism of some Dalradian pelites in the Buchan area,N.E. Scotland

Regional metamorphic zones, based on mineral assemblages in pelites, are presented for the Dalradian rocks of Aberdeenshire and Banffshire, in the type area of Buchan metamorphism; electron microprobe analyses of cordierite (C), staurolite (S), chlorite (Chl), biotite (B) and white mica (Ms) are reported for rocks from the classic sections of the Banffshire coast and the valley of the Ythan.A low grade biotite zone, separates two NE-SW trending sets of higher grade zones, in which the sequence s defined by the entry of cordierite, andalusite (A) and (in the west only) staurolite. The zones are characterised by the assemblages (with quartz and muscovite) B-Chl, C-B-Chl, A-C-B and S-A-B.The western sequence contains a transition towards higher pressure, Barrovian type, metamorphism. The isograds arise from continuous reactions affecting rocks of restricted bulk composition (M/FM). With increasing grade, there is a regular trend towards more magnesian ranges of composition for the assemblages C-B-Chl, A-C-B and finally (as P increases in the west), S-A-B. The isograds form when these assemblages intersect the most Fe⁺⁺-rich rock compositions present which occurs in each case when the biotite M/FM=40. A complex of divariant equilibria, derived for the system KFMASH, is used to model the natural reactions.     

Regional fluid and metal mobility in the Dalradian metamorphic belt,Southern Grampian Highlands,Scotland

A prominent set of veins was formed during post-metamorphic deformation of the Caledonian Dalradian metamorphic belt. These veins are concentrated in dilational zones in fold hinges, but apophyses follow schistosity and fold axial surface fractures. The veins are most common in the cores of regional structures, especially the Dalradian Downbend and consist of quartz, calcite, chlorite and metallic sulphides and oxides. Metals, including gold, have been concentrated in the veins. The fluid which formed the veins was low salinity (1–5 wt% NaCl and KCl) CO₂-bearing (3–16 wt% CO₂) water of metamorphic origin. The fluid varies slightly in composition within and between samples, but is essentially uniform in composition over several hundred km². Vein formation occurred at about 350±50 °C and 200–300 MPa pressure. Further quartz mineralization occurred in some dilational zones at lower temperatures (160–180 °C). This later mineralization was accompanied by CO₂ immiscibility. Dilution and oxidation of the metamorphic fluid occurred due to mixing with meteoric water as the rocks passed through the brittle-ductile transition. A similar metamorphic fluid is thought to have been responsible for gold mineralization in the nearby Tyndrum Fault at a later stage in the Dalradian uplift.     

Sources of rare earth elements in Appin Group limestones,Dalradian, north-east Scotland

Summary Rare earth elements (REE) have been determined in 15 samples from three metamorphosed limestone units of the Appin Group of the Dalradian of north-east Scotland. Total REE contents range from about 7 to about 50 ppm and the light REEs are slightly enriched compared with REE in the North American Shale Composite (NASC). In the more impure limestones, the dominant control on REE content was the clay mineral content in siliciclastic impurities derived from terrestrial sources. In the purer limestones, the correlation between REEs and iron is consistent with the well-documented relationship between iron and REEs in the aqueous environment. REE associated with terrestrial, iron-rich, flocculated organic colloids or marine, authigenic iron-manganese coats may well have contributed significantly to the REE contents. Weak Ce anomalies on NASC-normalised, REE variation diagrams in two samples with very low REE contents suggest a marine influence on the REE distribution.

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Die Quelle von Seltenen Erden in Kalken der Appin Gruppe, Dalradians, NE Schottland

Zusammenfassung An 15 Proben aus metamorphen Kalken der Appin Gruppe der Dalradians NE Schottlands wurde die Zusammensetzung der Seltenen Erden (REE) bestimmt. Der Gesamtgehalt an REE variiert von 7 bis 50 ppm, wobei die leichten REE im Vergleich zum North American Shale Composite (NASC) leicht angereichert sind. In unreinen Kalken wird der REE-Gehalt vom Tonmineralanteil der silikatisch-klastischen Verunreinigungen, die einer terrestrischen Quelle entstammen, kontrolliert. In reinen Karbonatgesteinen besteht eine Korrelation zwischen den REE und Fe, eine Beziehung, die für ein wässriges Milieu bereits bereits gut dokumentiert ist. REEs, die mit terrrestrischen, Fe-reichen, ausgeflockten organischen Kolloiden oder marinen, authigen gebildeten Fe-Mn Überzügen assoziiert sind, könnten beträchtlich zu den REE Gehalten beitragen. Schwache, in auf NASC normalisierten REE-Diagrammen erkennbare Ce-Anomalien von zwei Proben, lassen einen marinen Einfluß vermuten.

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With 5 Figures     

Sources of rare earth elements in Appin Group limestones,Dalradian, north-east Scotland

Summary Rare earth elements (REE) have been determined in 15 samples from three metamorphosed limestone units of the Appin Group of the Dalradian of north-east Scotland. Total REE contents range from about 7 to about 50 ppm and the light REEs are slightly enriched compared with REE in the North American Shale Composite (NASC). In the more impure limestones, the dominant control on REE content was the clay mineral content in siliciclastic impurities derived from terrestrial sources. In the purer limestones, the correlation between REEs and iron is consistent with the well-documented relationship between iron and REEs in the aqueous environment. REE associated with terrestrial, iron-rich, flocculated organic colloids or marine, authigenic iron-manganese coats may well have contributed significantly to the REE contents. Weak Ce anomalies on NASC-normalised, REE variation diagrams in two samples with very low REE contents suggest a marine influence on the REE distribution.

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Die Quelle von seltenen erden in kalken der Appin Gruppe, Dalradians, NE Schottland

Zusammenfassung An 15 Proben aus metamorphen Kalken der Appin Gruppe der Dalradians NE Schottlands wurden die Seltenen Erden (REE) bestimmt. Der Gesamtgehalt an REE variiert von 7 bis 50 ppm, wobei die leichten REE im Vergleich zum North American Shale Composite (NASC) leicht angereichert sind. In unreinen Kalken wird der REE-Gehalt vom Tonmineralanteil der silikatisch-klastischen Verunreinigungen, die einer terrestrischen Quelle entstammen, kontrolliert. In reinen Karbonatgesteinen besteht eine Korrelation zwischen den REE und Fe, eine Beziehung, die für ein wässriges Milieu bereits bereits gut dokumentiert ist. REEs, die mit terrestrischen, Fe-reichen, ausgeflockten organischen Kolloiden oder marinen, authigen gebildeten Fe-Mn Überzügen assoziiert sind, könnten beträchtlich zu den REE Gehalten beitragen. Schwache, in auf NASC normalisierten REE-Diagrammen erkennbare Ce-Anomalien von zwei Proben, lassen einen marinen Einfluß vermuten.

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The Managing Editor regrets that the complete text of this paper has already been published in Mineral Petrol 49: 27–44 (1993)     

Infiltration of Aqueous Fluid and High Fluid: Rock Ratios During Greenschist Facies Metamorphism: A Reply

Wood & Graham (1986) suggest that fluid: rock ratios ofFerry (1984) were over-estimated because the temperature ofthe biotite isograd, inferred from biotite-garnet and calcite-dolomitegeothermometry, was underestimated by {small tilde}40?C. Wood& Graham's critique of calcite-dolomite geothermometry isincomplete because it fails to account for the effect of MnCO₃substitutions in calcite on estimated temperatures. New datathat consider the effects of both FeCO₃ and MnCO₃ substitutionssuggest that published calcite-dolomite temperatures need nosignificant correction. Their proposed correction to biotite-garnettemperatures, based on the garnet solid solution model of Ganguly& Saxena (1984), has an uncertainty of at least 100 percent and is not significantly different from zero. An empiricalscheme that corrects for the effects of grossular and spessartinesubstitution in garnet on estimated temperature, along withthe large uncertainty in Wood and Graham's proposed correction,suggest that published biotite-garnet temperatures also needno significant revision. The preferred temperature for the biotiteisograd remains {small tilde}400?C. In turn, the preferred estimatesof fluid: rock ratios remain unchanged; pelitic phyllites interactedwith at least 1-2 rock volumes fluid during the biotite-formingreaction at 400?C. Varied geologic, petrologic, and isotopic data are reviewedthat support fluid:rock ratios > 1 during low-grade metamorphismboth in south-central Maine and worldwide. Chemical interactionbetween rocks and fluids that are initially out of equilibriummay be an essential driving force behind many instances of low-graderegional metamorphism. Fluid:rock ratios > 1 and recent stableisotope studies should encourage serious consideration of amulti-pass model for metamorphic fluid flow.     

Infiltration of Aqueous Fluid and High Fluid: Rock Ratios During Greenschist Facies Metamorphism: A Discussion

Ferry's (1984) analysis of the biotite isograd in pelitic schistsof the Waterville Formation (south-central Maine, U.S.A.) ledto the conclusion that metamorphism had been caused by infiltrationof 1–2 rock volumes of aqueous fluid. We find that thisimportant observation is extremely sensitive to the assumedtemperature of metamorphism and to corresponding uncertaintiesin the thermodynamic data and solution assumptions. Uncertaintiesin the experimental calibrations of the geothermometers areon the order of ? 30?C. In addition, an analysis of the effectsof minor substituents on calcite-dolomite and garnet-biotitegeothermometers indicates that Ferry's (1980) temperatures areabout 40?C too low in the garnet zone. Correcting the phaseequilibria to higher temperatures by this latter amount lowersfluid:rock ratios by an order of magnitude to about 0?1:1. Sincesmall uncertainties have such great effects it is clearly importantto perform careful uncertainty analyses before using Ferry'sapproach to draw wide-ranging conclusions about fluid-rock interactions.Given a 40?C upward revision of temperature it is not necessaryto invoke pervasive infiltration of aqueous fluid as the majoragent of metamorphism. With these low fluid:rock ratios thewater source could reasonably be a thin sequence of underlyingmetapelites and/or the granitic intrusives which accompaniedthe Acadian orogeny.