Transition from the Zeolite to Prehnite-Pumpellyite Facies in the Karmutsen Metabasites, Vancouver Island, British Columbia

The upper Triassic Karmutsen metabasites from northeast VancouverIsland, B.C., are thermally metamorphosed by the intrusion ofthe Coast Range Batholith. The amygdaloidal metabasites developedin the outer portion of the contact aureole show a progressivemetamorphism from zeolite to prehnite-pumpellyite facies. Thesize of an equilibrium domain is extremely small for these metabasites,and the individual amygdule assemblages are assumed to be inequilibrium. Two major calcite-free assemblages (+chlorite+quartz)are characteristic: (i) laumontite+pumpellyite+epidote in thezeolite facies and (ii) prehnite+pumpellyite+epidote in theprehnite-pumpellyite facies. The assemblages and compositionsof Ca-Al silicates are chemographically and theoretically interpretedon the basis of the predicted P-T grid for the model basalticsystem, CaO-MgO-A1₂O₃-Fe₂O₃-SiO₂-H₂O. The results indicate:(1) local equilibrium has been approached in mineral assemblagesand compositions; (2) the X_Fe³⁺ values in the coexisting Ca-Alsilicates decrease from epidote, through pumpellyite to prehnite;(3) with increasing metamorphic grade, the Fe³⁺ contents ofepidotes in reaction assemblages decrease in the zeolite facies,then increase in the prehnite-pumpellyite facies rocks. Suchvariations in the assemblages and mineral compositions are controlledby a sequence of continuous and discontinuous reactions, andallow delineation of T-X_Fe³⁺ relations at constant pressure.The transition from the zeolite to prehnite-pumpellyite faciesof the Karmutsen metabasites is defined by a discontinuous reaction:0·18 laumontite+pumpellyite+0·15 quartz = 1·31prehnite+ 0·78 epidote+0·2 chlorite+ 1·72H₂O, where the X_Fe³⁺ values of prehnite, pumpellyite and epidoteare 0·03, 0·10 and 0·18, respectively.These values together with available thermodynamic data andour preliminary experimental data are used to calculate theP-T condition for the discontinuous reaction as P = 1·1±0·5 kb and T = 190±30°C. The effectsof pressure on the upper stability of the zeolite facies assemblagesare discussed utilizing T-X_Fe³⁺ diagrams. The stability of thelaumontite-bearing assemblages for the zeolite facies metamorphismof basaltic rocks may be defined by either continuous or discontinuousreactions depending on the imposed metamorphic field gradient.Hence, the zeolite and prehnite-pumpellyite facies transitionboundary is multivariant.     

Secondary Ca–Al silicates in plutonic rocks: implications for their cooling history

Secondary Ca-Al silicates are used to constrain the P-T-x conditions of the very early post-magmatic stage of the intermediate to basic Hercynian plutonic complexes of Charroux-Civray (NW Massif Central, France) and Fichtelgebirge (NE Bavaria, Germany). The secondary Ca-Al silicates hydrogarnet, prehnite, pumpellyite, epidote and laumontite form lenses within unaltered or only slightly chloritized biotite. Hydrogarnet as the first occurring Ca-Al silicate phase crystallizes at temperatures above 340 °C. The common paragenesis prehnite + pumpellyite post-dates hydrogarnet and indicates rather narrow ranges of temperature (200-280 °C) and pressure (2-3 kbar). Laumontite is formed at the end of Ca-Al silicate crystallization (180-260 °C, 1-3 kbar), mostly in small fractures in association with prehnite and adularia. The observed crystallization sequence of the Ca-Al silicates and their stabilities define a retrograde alteration path for the plutonic rocks. The Ca-Al silicate assemblage results from an early pervasive alteration of the plutonic rocks by low X_CO2 fluids during post-magmatic cooling. Subsolidus cooling starts at about 4 kbar at solidus temperatures as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data, and continues under slightly decreasing pressure (uplift) down to 2-3 kbar at 200-280 °C (prehnite-pumpellyite paragenesis). This shows that Ca-Al silicate assemblages may be a unique tool to constrain the P-T conditions of the subsolidus cooling of intermediate to basic plutonic bodies.     

Actinolite-forming reaction at low pressure and the role of Fe2+-Mg substitution

The 6km-thick Karmutsen metabasites, exposed over much of Vancouver Island, were thermally metamorphosed by intrusions of Jurassic granodiorite and granite. Observation of about 800 thin sections shows that the metabasites provide a complete succession of mineral assemblages ranging from the zeolite to pyroxene hornfels facies around the intrusion. The reaction leading to the appearance of actinolite, which is the facies boundary between prehnite-pumpellyite and prehnite-actinolite facies, was examined using calcite-free Karmutsen metabasites collected from the route along the Elk river. In the prehnite-pumpellyite facies, X _Fe3+[Fe³⁺/(Fe³⁺+Al)] in prehnite, pumpellyite and epidote buffered by the four-phase assemblage prehnite+pumpellyite+epidote+chlorite systematically decreases with increasing metamorphic grade. Such a trend is the reverse of that proposed by Cho et al. (1986); this may be related to the higher in the Mt. Menzies area. The actinolite-forming reaction depends on the value of X ^Fe3+ in pumpellyite. If using a low value of ^Fe3+, 3.89 Pr(0.06)+0.48 Ep(0.26)+0.60 Chl+H₂O=2.10 Pm (0.08)+0.17 Act+0.88 Qz is delineated. The number in parentheses stands for the X _Fe3+value in Ca-Al silicates. On the other hand, replacing the X _Fe3+ of 0.08 in pumpellyite with a higher X _Fe3+ value (0.24) changes the reaction to 0.41 Pm+0.02 Chl+0.42 Qz=0.11 Pr+0.62 Ep+0.10 Act+H₂O. The first (hydration) reaction forms pumpellyite and actinolite on the high-temperature side, whereas the second (dehydration) reaction consumes pumpellyite to form prehnite, epidote and actinolite. The former reaction seems to explain the textural relationship of Ca-Al silicates in the study area. However, actinolite-forming reaction changes to a different reaction depending on the compositions of the participating minerals, although in the other area even physical conditions may be similar to those in the study area. Chemographic analysis of phase relations in the PrA facies indicates that the appearance of prehnite depends strongly on the bulk FeO/MgO ratio: this may explain the rarity of prehnite in common metabasites in spite of the expected dominant occurrence in the conventional pseudo-quaternary (Ca-Al-Fe³⁺-FM) system. An increasing FeO/MgO ratio stabilizes the Pr+Act assemblage and reduces the stability of the Pm+Act one. Therefore, the definition of pumpellyite-actinolite facies should include not only Pm+Act but also the absence of Pr+Act assemblages. In addition to the possible role of high (Cho and Liou 1987) and/or high to mask the appearance of prehnite, the effect of the FeO/MgO ratio is emphasized.     

Phase equilibria among pumpellyite,lawsonite, epidote and associated minerals in low grade metamorphic rocks

Phase relations of pumpellyite, epidote, lawsonite, CaCO₃, paragonite, actinolite, crossite and iron oxide are analysed on an Al-Ca-Fe³⁺ diagram in which all minerals are projected from quartz, albite or Jadeite, chlorite and fluid. Fe²⁺ and Mg are treated as a single component because variation in Fe²⁺/Mg has little effect on the stability of phases on the diagram. Comparison of assemblages in the Franciscan, Shuksan, Sanbagawa, New Caledonia, Southern Italian, and Otago metamorphic terranes reveals several reactions, useful for construction of a petrogenetic grid:

1. lawsonite+crossite + paragonite = epidote+chlorite + albite + quartz + H₂O
2. lawsonite + crossite = pumpellyite + epidote + chlorite + albite+ quartz + H₂O
3. crossite + pumpellyite + quartz = epidote + actinolite + albite + chlorite + H₂O
4. crossite + epidote + quartz = actinolite + hematite + albite + chlorite + H₂O
5. calcite + epidote + chlorite + quartz = pumpellyite + actinolite + H₂O + CO₂
6. pumpellyite + chlorite + quartz = epidote + actinolite + H₂O

     

A new petrogenetic grid for low-grade metabasites

Abstract We have used internally-consistent thermodynamic data to present calculated phase equilibria for the system Na₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O (NCMASH), in the range 0–500° C and 0.1–10 kbar, involving the phases anorthite, glaucophane, grossular, heulandite, jadeite, laumontite, lawsonite, paragonite, prehnite, pumpellyite, stilbite, tremolite, wairakite, zoisite with excess albite, clinochlore, quartz and pure water. Average activity terms derived from published mineral chemical data were included for clinochlore, glaucophane, prehnite, pumpellyite, tremolite, and zoisite. The new petrogenetic grid delineates stability fields and parageneses of common index minerals in zeolite, prehniteactinolite, prehnite-pumpellyite, pumpellyite-actinolite, blueschist and greenschist facies metabasites. The stability fields of mineral assemblages containing prehnite, pumpellyite, epidote, actinolite (+ albite + chlorite + quartz) were analysed in some detail, using activity data calculated from five specific samples. For example, the prehnite-actinolite facies covers a P-T field ranging from about 220 to 320° C at pressures below 4.5 kbar. The transition from the prehnite-actinolite and pumpellyite-actinolite to greenschist facies occurs at about 250–300° C at 1–3 kbar and at about 250–350° C at 3–8 kbar. P-T fields of individual facies overlap considerably due to variations in chemical composition.     

Fluid-mineral equilibria in prehnite-pumpellyite to greenschist facies metabasites near Flin Flon, Manitoba, Canada: implications for petrogenetic grids

A sequence of regional metamorphic isograds indicating a range from prehnite-pumpellyite to lower amphibolite facies was mapped in metabasites near Flin Flon, Manitoba. The lowest grade rocks contain prehnite + pumpellyite and are cut by younger brittle faults containing epidote + chlorite + calcite. Isobaric temperature- X _CO2 and pressure-temperature (constant X _CO2) diagrams were calculated to quantify the effects of CO₂ in the metamorphic fluid on the stability of prehnite-pumpellyite facies minerals in metabasites containing excess quartz and chlorite. Prehnite and, to a lesser extent, pumpellyite are stable only in fluids with X _co2 <0.002. For X _co2>0.002, epidote + chlorite + calcite assemblages are stable. Our calculated phase relations are consistent with regional metamorphism in the Flin Flon area in the presence of an H₂O-rich fluid and a more CO₂-rich fluid in the later fault zones. We believe that the potential effects of small amounts of CO₂ in the metamorphic fluid should be assessed when considering the pressure-temperature implications of mineral assemblages in low-grade metabasites.     

Low-grade Metamorphism of the Karmutsen Volcanics, Vancouver Island, British Columbia

Low-variance assemblages occurring within amygdules of Karmutsenlavas from the Elk Creek and Upper Campbell Lake areas, VancouverIsland, British Columbia, provide important constraints on thepressure and temperature of metamorphism as well as on the compositionof the attendant fluid. The P-T stability of the assemblagesepidote-muscovite-K-feldspar-prehnite and epidote-prehnite-quartz-wairakitecoupled with mean isochores derived from homogenization temperaturesof H₂O inclusions within amygdaloidal quartz indicate that theUpper Campbell Lake area was subjected to metamorphism at 1?5kb (?0?5 kb), 260 ?C (? 15?C) and the Elk Creek area at somewhatlower P or higher T. Isobaric T-a(CO₂) diagrams show that the occurrence of epidote-oligoclase,prehnite-orthoclase-albite, and prehnite-andesine assemblagescollected from the Elk Creek area is consistent with the P-Tconstraints and that these assemblages formed in water-richfluids containing very low concentrations of CO₂. The presenceof Ca-zeolite-epidote assemblages in the Upper Campbell Lakearea is also compatible with P-T estimates. The consistencyof epidote and prehnite rim compositions in low-variance assemblagesand the lack of incompatible phases in these assemblages demonstratethat equilibrium was obtained on limited domains within amygdules. Because epidote and prehnite compositions in low-variance assemblagesare very sensitive to changes in concentration of CO2, low-varianceassemblages involving these phases can serve as monitors offluid composition. It is postulated that low-variance assemblagesin Karmutsen flows originated by reaction of previously formed,high-variance assemblages with infiltrating CO₂-bearing aqueousfluids during a subsequent hydrothermal event. These fluidspreferentially exploited more permeable amygdaloidal portionsof the Karmutsen flows. The low-variance assemblages not onlyrecord the extremely H₂O-rich composition of the permeatingfluid, but also outline the paths the fluid took. ^* Offprint requests to B. R. Frost     

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.     

Reactions Leading to the Disappearance of Pumpellyite in Low-grade Metamorphic Rocks of the Sanbagawa Metamorphic Belt in Central Shikoku, Japan

The major mineral assemblages of the metabasites of the Omoiji-Nagasawaarea in central Shikoku are hematite+epidote+chlorite+actinolite,riebeckitic actinolite+epidote+chlorite, epidote+chlorite+actinolite,and pumpellyite+epidote+chlorite+actinolite. The constituentminerals are often heterogeneous and assemblages in the fieldof a thin section sometimes do not obey the phase rule, butif grains apparently in non-equilibrium with others are excludedand domains of chemical equilibrium are appropriately chosenthe assemblages approximately obey the phase rule. The stability of hematite, pumpellyite, and epidote associatedwith chlorite and actinolite can be dealt with in terms of aternary system with appropriate excess phases. By fixing theFe²⁺/(Fe²⁺ +Mg) ratio of chlorite, it is dealt with in termsof stability relations in the system Ca₂Al₃Si₃O₁₂(OH)–Ca₂AlFe₂Si₃O₁₂(OH)with excess chlorite, actinolite, quartz, and controlled P_H2O.The maximum and minimum Fe³⁺ contents of epidote in this modelsystem are determined by hematite+epidote+chlorite+actinoliteand pumpellyite+epidote+chlorite+actinolite assemblages. Themaximum Fe³⁺ of the three phase assemblage epidote+chlorite+actinoliteis insensitive to temperature, but the minimum Fe³⁺ contentof epidote is sensitive to temperature and can be used to definethe metamorphic grade by a continuous quantity related to temperature.The phase relations expected for the model system are in goodagreement with the parageneses of the Sanbagawa terrain in centralShikoku and offer an explanation to the rule of Miyashiro &Seki (1958a) that the compositional range of epidote enlargeswith increasing temperature. The model also makes it possibleto estimate semi-quantitatively the temperature range in whichthe assemblage pumpellyite+epidote+chlorite+actinolite is stable.The possible maximum range is about 120 ?C, but the assemblageis stable in metabasite only for about 90 ?C. The higher temperaturelimit of the pumpellyite-actinolite facies defined by the disappearanceof pumpellyite in metabasite corresponds to the temperatureat which epidote with Fe³⁺/(Fe³⁺ +Al) = 0.10 0.15 coexistswith pumpellyite, actinolite, and chlorite. The compositions of epidotes in the metabasites of the Omoiji-Nagasawaarea cluster around Fe³⁺/(Fe³⁺ +Al) = 0.33. The grade of thisarea is close to the lower temperature stability limit of thepumpellyite+epidote+chlorite+actinolite assemblage.     

Synthesis and Stability Relations of Mg--Al Pumpellyite, Ca4Al5MgSi6O21(OH)7

Hydrothermal synthesis and investigations of stability relationsof Mg—Al pumpellyite were conducted using high-pressurecold-seal apparatus over the temperature range 250–600°C and 2–8 kb P_fluid. Mg—Al pumpellyite Ca₄Al₅MgSi₆O₂₁(OH)₇was synthesized from partially crystalline gel mixtures of stoichiometriccomposition at 275–410 °C, 6–9 kb P_fluid, andruns of 7–90 days. Pure monomineralic synthetic Mg—Alpumpellyite has refractive index n_ß = 1.624 (2) andcell dimensions = 8.825 (8) Á, b = 5.875 (5) Á,c = 19.10 (1) Á, and ß = 97.39 (7)°. The high temperature assemblage of the equivalent bulk compositionconsists of clinozoisite, hydrogrossular/grossular, aluminousseptechlorite/chlorite, quartz, and H₂O. Hydrogrossular wassynthesized in the presence of quartz at 8 kb from 400–500°C, and hydrogrossular + quartz are unstable with respectto grossular + H₂O at 400 °C and 8 kb P_fluid. At 8 kb P_fluid,aluminous septechlorite forms at temperatures below 500 °Cwhereas aluminous 14 Á chlorite crystallizes at 500–600°C. The equilibrium relations of Mg—Al pumpellyite were determinedusing subequal mixtures of synthetic Mg—Al pumpellyiteand its high temperature assemblage. The reaction 9 Mg—Alpumpellyite = 9 clinozoisite + 6 grossular + 2 chlorite + 4quartz + 19 H₂O occurs at temperatures of 390 °C at 8 kb,368 °C at 5 kb, and near 325 °C at 2 kb P_fluid. Thereversal data yield an approximate value of –3141 joules/mole°K for the standard entropy of formation for the syntheticMg—Al pumpellyite. The Schreinemakers' relations for pumpellyite, prehnite, clinozoisite,tremolite, grossular, and amesite in the presence of excessquartz and fluid were constructed in the pseudo-ternary systemCaO–Al₂O₃–MgO(SiO₂–H₂O). The results, togetherwith reconnaissance experiments on the reaction 4 Mg—Alpumpellyite + 2 quartz = 8 prehnite + aluminous septechlorite+ 2 H₂O, locate the invariant point [TR] at approximately 5.7kb P_fluid and 375 °C. The results of the present study arenot compatible with previous experimental data on the invariantpoint [GR]. The P–T oriented phase relations are used to interpretsome natural parageneses developed in low-grade metabasalticrocks recrystallized under conditions of low _co2. The high-temperaturestability relations of Mg—Al pumpellyite are useful todenote the onset of greenschist facies metamorphism in rocksof basaltic composition.     

Petrology of an Andalusite-Type Regional Metamorphic Terrane, Panamint Mountains, California

The terrane in the Panamint Mountains, California, was regionallymetamorphosed under low-pressure conditions and subsequentlyunderwent retrograde metamorphism. Prograde metamorphic isogradsthat mark the stability of tremolite + calcite, diopside, andsillimanite indicate a westward increase in grade. The studywas undertaken to determine the effects of the addition of Caon the types of assemblages that may occur in pelitic schists,to contribute to the understanding of the stability limits inP – T – aH₂O – X_Fe of the pelitic assemblagechlorite + muscovite + quartz, and to estimate the change inenvironment from prograde to retrograde metamorphism. Peliticassemblages are characterized by andalusite + biotite + stauroliteand andalusite + biotite + cordierite. Within a small changein grade, chlorite breaks down over nearly the entire rangein Mg/(Mg + Fe) to biotite + aluminous mineral. Chlorite withMg/(Mg + Fe) = 0.55 is stable to the highest grade, and thegeneralized terminal reaction is chlorite + muscovite + quartz= andalusite + biotite + cordierite + H₂O. Calcic schists arecharacterized by the assemblage epidote + muscovite + quartz+ chlorite + actinolite + biotite + calcite + plagioclase atlow grades and by epidote + muscovite + quartz + garnet + hornblende+ biotite + calcite + plagioclase at high grades. Epidote doesnot coexist with any AFM phase that is more aluminous than garnetor chlorite. Lithostatic pressure ranged from 2.3 kb to 3.0kb. During prograde-metamorphism temperatures ranged from lessthan 400° to nearly 700°C, and X_H2O (assuming P_H2O +P_CO3 = P_total) is estimated to be 0.25 in siliceous dolomite,0.8 in pelitic schist, and 1.0 in calcic schist. Temperatureduring retrograde metamorphism was 450° ± 50°C,and all fluid were H₂O-rich. A flux of H₂O-rich fluid duringfolding is believed to have caused retrograde metamorphism.The petrogenetic grid of Albee (1965b) is modified to positionthe (A, Cd) invariant point relative to the aluminosilicatetriple point, which allows the comparison of facies series thatinvolve different chloritoid-reactions.     

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.     

A model for phase equilibria in the prehnite-pumpellyite facies

Using the method of Schreinemakers, along with other thermodynamic considerations, a phase diagram for the system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂O was constructed. The phases prehnite, pumpellyite, calcite, chlorite, dolomite, quartz, tremolite, talc, zoisite, grossularite and vapor were considered in this construction. The results indicate that prehnite-pumpellyite facies mineral assemblages will only exist in equilibrium with a vapor phase in which the mole fraction of CO₂ is less than 0.2 at 1 kb, and less than 0.15 at 2 kb. Although talc could theoretically be a stable phase under these conditions, its common absence from rocks of this facies probably results from the existence of an enantiomorphic point which makes tremolite-calcite-CO₂ the stable assemblage at low X _{CO 2}, and the compositionally equivalent talc-calcite-CO₂ assemblage stable at moderate X _{CO 2}.     

The Garnet+Hornblende Isograd in Calcic Schists from an Andalusite-Type Regional Metamorphic Terrain, Panamint Mountains, California

Calcic schists in the andalusite-type regional metamorphic terrainin the Panamint Mountains, California, contain the low-varianceassemblage quartz+epidote+muscovite+biotite+calcic amphibole+chlorite+plagioclase+spheneat low grade. Near the sillimanite isograd, chlorite in thisassemblage is replaced by garnet. The low variance in many calcicschists allows the determination of the nature of the reactionthat resulted in the coexistence of garnet+hornblende. A graphicalanalysis of the mineral assemblages shows that the reactioncan not be of the form biotite+epidote+chlorite+plagioclase+quartz=garnet+hornblende+muscovite+sphene+H₂Obecause garnet+chlorite never coexisted during metamorphismand the chlorite-bearing and garnet-bearing phase volumes donot overlap. The compositions of the minerals show that withincreasing grade amphibole changed from actinolite to pargasitichornblende with no apparent miscibility gap, the partitioningof Fe and Mg between chlorite and hornblende changed from K_D(Mg/Fe, chl&amp) < 1 to K_D > 1, the partitioning betweenbiotite and hornblende changed from K_D (Mg/Fe, bio/amp) <1 in chlorite-zone samples to K_D > 1 in garnet + hornblende-zonesamples, and the transition to the garnet-bearing assemblageoccurred when the composition of plagioclase was between An₅₅and An₈₀. Both the graphical analysis and an analytical analysisof the compositions of the minerals using simplified componentsderived from the natural mineral compositions indicate thatat the garnet+hornblende isograd the composition of hornblendewas colinear with that of plagioclase and biotite, as projectedfrom quartz, epidote, muscovite, and H₂O. During progressivemetamorphism, chlorite+biotite+epidote+quartz continuously brokedown to form hornblende+muscovite+sphene until the degeneracywas reached. At that point, tie lines from hornblende couldextend to garnet without allowing garnet to coexist with chlorite.Thus, the garnet+hornblende isograd was established throughcontinuous reactions within the chlorite-grade assemblage ratherthan through a discontinuous reaction. In this type of isograd,the low-grade diagnostic assemblage occurs only in Mg-rich rocks;whereas the high-grade assemblage occurs only in Fe-rich rocks.This relation accounts for the restricted occurrence of garnet+hornblendeassemblage in low-pressure terrains. In Barrovian terrains,garnet+chlorite commonly occurs, and the first appearana ofgarnet+hornblende can simply result from the continuous shiftof the garnet+chlorite tie line to Mg-rich compositions.     

Mineral assemblages and phase equilibria of metabasites from the prehnite–pumpellyite to amphibolite facies,with the Flin Flon Greenstone Belt (Manitoba) as a type example

An exceptionally well-exposed part of the Flin Flon Greenstone Belt (Manitoba/Saskatchewan) is used to characterize the mineral assemblage evolution associated with prehnite–pumpellyite through amphibolite facies metamorphism of basalts. Data from these rocks are combined with a large literature data set to assess the ability of current thermodynamic models to reproduce natural patterns, evaluate the use of metabasic rocks at these grades to estimate pressure–temperature (P–T) conditions of metamorphism, and to comment on the metamorphic devolatilization that occurs. At Flin Flon, five major isograds (actinolite-in, prehnite- and pumpellyite-out, hornblende-in, oligoclase-in, and actinolite-out) collectively represent passage from prehnite–pumpellyite to lower amphibolite facies conditions. The evolution in mineral assemblages occurs in two narrow (~1,000 m) zones: the prehnite–pumpellyite to greenschist facies (PP-GS) transition and greenschist to amphibolite facies (GS-AM) transition. Across the GS-AM transition, significant increases in the hornblende and oligoclase proportions occur at the expense of actinolite, albite, chlorite, and titanite, whereas there is little change in the proportions of epidote. The majority of this mineral transformation occurs above the oligoclase-in isograd within the hornblende–actinolite–oligoclase zone. Comparison with thermodynamic modelling results suggests data set 5 (DS5) of Holland and Powell (1998, Journal of Metamorphic Geology, 16 (3):309–343) and associated activity–composition (a–x) models is generally successful in reproducing natural observations, whereas data set 6 (DS6) (Holland & Powell, 2011, Journal of Metamorphic Geology, 29 (3):333–383) and associated a–x models fail to reproduce the observed mineral isograds and compositions. When the data from Flin Flon are combined with data from the literature, two main pressure-sensitive facies series for metabasites are revealed, based on prograde passage below or above a hornblende–albite bathograd at ~3.3 kbar: a low-pressure ‘actinolite–oligoclase type’ facies series, characterized by the appearance of oligoclase before hornblende, and a moderate- to high-pressure ‘hornblende–albite type’ facies series, characterized by the appearance of hornblende before oligoclase. Concerning the PP-GS transition, the mineral assemblage evolution in Flin Flon suggests it occurs over a small zone (<1,000 m), in which assemblages containing true transitional assemblages (prehnite and/or pumpellyite coexisting with actinolite) are rare. This contrasts with thermodynamic modelling, using either DS5 or DS6, which predicts a wide PP-GS transition involving the progressive appearance of epidote and actinolite and disappearance of pumpellyite and prehnite. Patterns of mineral assemblages and thermodynamic modelling suggest a useful bathograd (‘CHEPPAQ bathograd’), separating prehnite–pumpellyite-bearing assemblages at low pressures and pumpellyite–actinolite-bearing assemblages at higher pressures, occurs at ~2.3 to 2.6 kbar. Observations from the Flin Flon sequence suggests devolatilization across the GS-AM transition (average: ~1.8 wt% H₂O) occurs over a very narrow interval within the actinolite–hornblende–oligoclase zone, associated with the loss of >75% of the total chlorite. By contrast, modelling of the GS-AM transition zone predicts more progressive dehydration of ~2 wt% H₂O over a >50°C interval. Observations from the field suggest devolatilization across the PP-GS transition occurs over a very narrow interval given the rarity of transitional assemblages. Modelling suggests fluid release of 1.0–1.4 wt% resulting from prehnite breakdown over a ~10°C interval. This fluid may not be entirely lost from the rock package due to involvement in the hydration of igneous mineralogy across the PP-GS transition as observed in the Flin Flon sequence.     

Description and interpretation of the composition of fluid and alteration mineralogy in the geothermal system,at Svartsengi,Iceland

The bulk composition and mineralogy of hydrothermally altered tholeiite, along with the composition and speciation of fluid, have been determined for a well-defined alteration zone at 240°C and 110 bars at Svartsengi, Iceland. Mass balances between the geothermal fluid and altered tholeiite, relative to a seawater/fresh water mixture and unaltered tholeiite, indicate the overall reaction per 1000 cm³ is: 1325 gm plagioclase + 1228 gm pyroxene + 215 gm oxide-minerals break down to form 685 gm chlorite + 636 gm albite + 441 gm quartz + 249 gm epidote + 266 gm calcite + 201 gm oxide-minerals + 15 gm pyrite, requiring an influx of 123 gm CO₂, 10 gm H₂S and 4 gm Na₂O and a release of 57 gm SiO₂, 35 gm FeO, 21 gm CaO, 8 gm MgO and 4 gm K₂O.Principal reactions, deduced from textural evidence, include Na-Ca exchange in plagioclase, precipitation of quartz, calcite and anhydrite, and formation of chlorite and epidote by reactions between groundmass minerals and fluid.Thermodynamic analyses of authigenic minerals and downhole fluid indicate that the fluid maintains a state close to equilibrium with the secondary mineral phases chlorite, epidote, albite, quartz, calcite, prehnite, anhydrite, pyrite and magnetite, whereas remnant primary labradorite and augite are out of equilibrium with the fluid.Water/rock ratios for the system are determined under a variety of assumptions. However, the open nature of the system makes comparisons with experimental and theoretical closed system studies ambiguous.     

Seafloor hydrothermal alteration at an Archaean mid-ocean ridge

A hydrothermally metamorphosed/altered greenstone complex capped by bedded cherts exposed in the North Pole, Pilbara Carton, Western Australia, is interpreted as an accretionary complex. It is distinctive in being characterised by both duplex structure and an oceanic crust stratigraphy. This complex is shown to represent an Archaean upper oceanic crust with a mid‐ocean ridge hydrothermal metamorphism that increases in grade stratigraphically downward. Three mineral zones have been defined; Zone A of the zeolite facies, the prehnite‐pumpellyite facies or the lower‐greenschist facies at high‐X_CO2 condition, Zone B of the greenschist facies, and Zone C of the greenschist/amphibolite transition facies. In Zone A metabasites, Ca‐Al silicates including Ca‐zeolites, prehnite and pumpellyite are absent and epidote/clinozoisite is extremely rare. Instead, abundant carbonates are present with chlorite suggesting high‐X_CO2 composition in the fluid. On the other hand, in Zones B and C metabasites, where Ca‐amphibole + epidote/clinozoisite + chlorite + Ca‐Na plagioclase are the dominant assemblages, carbonate is not identified. The metamorphic conditions boundary of Zones B/C were estimated to be about 350 °C at a pressure of <0.5 kbar. Fluid compositions coexisting with Archaean greenstones at the transition between Zones B and C were estimated by thermodynamic calculation in the CaFMASCH system (T = 350–370 °C, P = 150–1000 bar) at X_CO2 of 0.012–0.140, such values are higher than present‐day vent fluids collected near mid‐ocean ridges with low‐X_CO2 values, up to 0.005. The Archaean seawater depth at the mid‐ocean ridge was estimated to be 1600 m at X_CO2 = 0.06 using a depth‐to‐boiling point curve for a fluid. The carbonation due to high‐X_CO2 hydrothermal fluids occurred near the ridge‐axis before or was coincident with ridge metamorphism.     

Petrology of Franciscan Metabasites Along the Jadeite-Glaucophane Type Facies Series, Cazadero, California

The Cazadero blueschist allochthon lies within the Central MelangeBelt of the Franciscan assemblage in the northern Coast Rangeof California. Mineral compositions and assemblages of morethan 200 blueschists from Ward Creek were investigated. Theresults delineate lawsonite-, pumpellyite-, and epidote-zones.The lawsonite and pumpellyite zones are equivalent to the TypeII metabasites of Coleman & Lee (1963) and are characterizedby well-preserved igneous textures, relict augite, and pillowstructures, whereas epidote zone rocks are equivalent to theType III strongly deformed and schistose metabasites. Chlorite,phengite, aragonite, sphene, and minor quartz and albite areubiquitous. The lawsonite zone metabasites contain lawsonite ( < 3 wt.per cent Fe₂O₃), riebeckite-crossite, chlorite, and Ca-Na-pyroxene;some rocks have two distinct clinopyroxenes separated by a compositionalgap. The clinopyroxene of the lowest grade metabasites containsvery low X_jd. In pumpellyite zone metabasites, the most commonassemblages contain Pm + Cpx + Gl + Chl and some samples withhigher Al₂O₃ and/or Fe₂O₃ have Pm + Lw + Cpx + Chl, Actinolitejoins the above assemblage in the upper pumpellyite zone wherethe actinolite-glaucophane compositional gap is well defined.The epidote zone metabasites are characterized by the assemblagesEp + Cpx + two amphiboles + Chl, Lw + Pm + Act + Chl, and Ep+ Pm + two amphiboles + Chl depending on the Fe₂O₃ content ofthe rock. In the upper epidote zone, winchite appears, Fe-freelawsonite is stable, pumpellyite disappears and omphacite containsvery low Ac component. Therefore, the common assemblages areEp + winchite + Lw, and Lw + Omp + winchite. With further increasein metamorphic grade, epidote becomes Al-rich and lawsoniteis no longer stable. Hence Ep + winchite + omphacite ? garnetis characteristic. Mineral assemblages and paragenetic sequences delineate threediscontinuous reactions: (1) pumpellyite-in; (2) actinolite-in;and (3) epidote-in reactions. Using the temperatures estimatedby Taylor & Coleman (1968) and phase equilibria for Ca-Na-pyroxenes,the P–T positions of these reactions and the metamorphicgradient are located. All three metabasite zones occur withinthe aragonite stability field and are bounded by the maximumpressure curve of Ab = Jd + Qz and the maximum stabilities ofpumpellyite and lawsonite. The lawsonite zone appears to bestable at T below 200?C with a pressure range of 4–6?5kb; the pumpellyite zone between 200 and 290?C and the epidotezone above 290?C with pressure variation between 6?5 and 9 kb.The metamorphic field gradient appears to have a convex naturetowards higher pressure. A speculative model of underplatingseamounts is used to explain such feature.     

Metamorphism of Calcic Pelitic Schists, Strafford Dome, Vermont: Compositional Zoning and Reaction History

Four assemblages from calcic pelitic schists from South Strafford,Vermont, have been studied in detail to determine the relationshipbetween reaction history and compositional zoning of minerals.The lowest-grade assemblage is garnet + biotite + chlorite +plagioclase + epidote + quartz + muscovite + graphite + fluid.Along a path of isobaric heating, the net reaction is Chl +Ms + Ep + Gr = Grt + Bt + Pl + fluid. Garnet grows with decreasingFe/(Fe + Mg) and X_Spa, (from 0•2 to 0•05), X_Gra staysnearly constant between 0•20 and 0•25, and plagioclasegrows with X_An increasing from peristerite to 0•2–0•5. The subsequent evolution depends on whether chlorite or epidotereacts out first. If chlorite is removed from the assemblagefirst, the net reaction along an isobaric heating path becomesGrt + Ms + Ep + Qtz + Gr = Bt + Pl + fluid. X_An of plagioclaseincreases to 0•20–0•70, depending on the bulk-rockcomposition and changes in pressure and temperature. If epidoteis removed first, the assemblage becomes a simple pelite andthe net reaction becomes Chl + Pl + Ms + Qtz = Grt + Bt + H₂O.Plagioclase is consumed to provide Ca for growing garnet, andX_An, Fe/(Fe + Mg) of garnet, X_Gra, and X_Spa all decrease. Afterboth chlorite and epidote are removed, continued heating upto the metamorphic peak of {small tilde}600C produces littleprogress of the reaction Grt + Ms = Bt + Pl; and X_An increases. The four assemblages have been numerically modeled using theGibbs method starting with measured compositions. The modelssuccessfully predict the observed compositional zoning and trendsof mineral growth and consumption along the computed P–Tpaths. The models also predict the compositional mineral zoningthat would have resulted from other P–T paths. ^* Present address: Department of Geology, University of Alabama, Tuscaloosa, Alabama 35487     

A Petrographic and Mineralogical Study of Volcanic Rocks from the Mayaxueshan Area, North Qilian Fold Belt, NW China

The Ordovician volcanic rocks in the Mayaxueshan area have been pervasively altered or metamorphosed and contain abundant secondary minerals such as albite, chlorite, epidote, prehnite, pumpellyite, actinolite, titanite, quartz, and/or calcite. They were denoted as spilites or spilitic rocks in terms of their petrographic features and mineral assemblages. The metamorphic grades of the volcanic rocks are equivalent to that of the intercalated metaclastic rocks. This indicates that both the spilitic volcanic rocks and metaclastic rocks in the Mayaxueshan area have formed as a result of Caledonian regional metamorphism. We suggest that the previously denoted spilitic rocks or altered volcanic rocks should be re-denoted as metabasalts or metabasaltic rocks. The metamorphic grade of the volcanic rocks increases with their age: prehnite-pumpellyite facies for the upper part of the Middle Ordovician volcanic rocks, prehnite-pumpeilyite to lower greenschist facies for the lower part of the Middle Ordovician vol