Monazite-Xenotime Thermochronometry and Al2SiO5 Reaction Textures in the Picuris Range, Northern New Mexico, USA: New Evidence for a 1450-1400 Ma Orogenic Event

Al₂SiO₅ reaction textures in aluminous schist and quartziteof the northern Picuris range, north-central New Mexico, recorda paragenetic sequence of kyanite to sillimanite to andalusite,consistent with a clockwise P–T loop, with minor decompressionnear the Al₂SiO₅ triple-point. Peak metamorphic temperaturesare estimated at 510–525°C, at 4·0–4·2kbar. Kyanite and fibrolite are strongly deformed; some prismaticsillimanite, and all andalusite are relatively undeformed. Monaziteoccurs as inclusions within kyanite, mats of sillimanite andcentimetre-scale porphyroblasts of andalusite, and is typicallyaligned subparallel to the dominant regional foliation (S₀/S₁or S₂) and extension lineation (L₁). Back-scatter electron imagesand X-ray maps of monazite reveal distinct core, intermediateand rim compositional domains. Monazite–xenotime thermometryfrom the intermediate and rim domains yields temperatures of405–470°C (±50°C) and 500–520°C(±50°C), respectively, consistent with the progradeto peak metamorphic growth of monazite. In situ, ion microprobeanalyses from five monazites yield an upper intercept age of1417 ± 9 Ma. Near-concordant to concordant analyses yield²⁰⁷Pb–²⁰⁶Pb ages from 1434 ± 12 Ma (core) to 1390± 20 Ma (rim). We find no evidence of older regionalmetamorphism related to the 1650 Ma Mazatzal Orogeny. KEY WORDS: Al₂SiO₅; metamorphism; monazite; thermochronometry; triple-point     

Solid-Fluid Equilibria in the System KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HCl

Activity diagrams in the system KAlSi₃O₈-NaAlSi₃O₈-Al₂SiO₅-SiO₂-H₂O-HClhave been calculated in terms of a_K+/a_H+ and a_N+/a_H+ from existingexperimental data. They show the effect of temperature, pressure,and a_H2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, a_H2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al₂SiO₅+H₂O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO₂+2 K⁺=3 K-feldspar+2 H⁺ muscovite+6 SiO₂+3 Na⁺=3 Albite+K⁺+2 H⁺ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H⁺=3 Al₂SiO₅+3 SiO₂+3 H₂O+2 K⁺ is favored at high temperature and pressure and low a_H2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.     

Mineralogy, Petrology, and Oxygen Isotopic Geochemistry of the Clough Formation, Black Mountain, Western New Hampshire, U.S.A.

The rocks of the Clough Formation, Black Mountain, New Hampshire,were regionally metamorphosed at 5.5 (±0.5) kb and 495°± 10 °C during the Acadian orogeny. Mineral assemblagesattained chemical equilibrium during metamorphism on the scaleof single sedimentary beds up to 1 m thick. An aqueous, intergranular,metamorphic fluid was probably present; however, the concentrationsof the species H₂O, H₂, and O₂ as well as the abundance of ¹⁸Oin the fluid varied from bed to bed. Neither isobaric nor polybaricosmotic equilibrium of H2 was attained between sedimentary beds.Fluid composition was controlled in each bed by the inherentbuffer capacity of the solid phases. Despite the effects ofprogressive dehydration during metamorphism, the buffer capacitiesof the mineral assemblages were sufficiently great that vestigesof premetamorphic heterogeneity of volatile components havebeen preserved.     

The Stability of Andradite, Hedenbergite, and Related Minerals in the System Ca--Fe--Si--O--H

Phase relations for the bulk compositions 3CaO·2FeO_x·3SiO₂+excessH₂O and CaO·FeO_x·2SiO₂+excess H₂O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO₂. Andradite, Ca₃Fe³⁺₂Si₃O₁₂, synthesized above 550 °C hasan average unit cell edge, a_o, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, a_o increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars P_fluid andradite is stable above an f_O2of 10¹⁵ bar at 800 °C and 10-³² bar at 400 °C. At lowerf_O2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe²⁺SiO₄)+ wollastonite and kirschsteinite+xonotlite (Ca₆Si₆O₁₇(OH)₂). Synthetic hedenbergite, CaFe²⁺Si₂O₆, has average unit cell dimensionsof a_o = 9.857± 0.004 Å, b_o = 9.033±0.002Å, c_o = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars P_fiuid, hedenbergite is stable below an f_O2 of10-¹³ bar at 800 °C and 10-²⁸ bar at 400 °C. Above thesef_O2 values, hedenbergite+O₂ breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the f_O2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H₂O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.     

The Effects of Small Amounts of H2O, CO2 and Na2O on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} H2O {+/-} CO2 {+/-} Na2O at 1{middle dot}1 GPa

The effects of small amounts of H₂O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al₂O₃–SiO₂ ±Na₂O ± CO₂ have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H₂O are to decreasethe melting temperature by 45°C per wt % H₂O in the melt,to increase the Al₂O₃ of the melts, decrease MgO and CaO, andleave SiO₂ approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO₂ are insignificantat zero H₂O, but become noticeable as H₂O increases, tendingto counteract the H₂O. The interaction between H₂O and CO₂ causesthe solubility of CO₂ at vapour saturation to increase withincreasing H₂O, for small amounts of H₂O. Neglect of the influenceof CO₂ in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H₂O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K₂O, i.e. increasing H₂O or K₂O leads to quartz-normativecompositions, but increasing Na₂O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H₂O; CO₂; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al₂O₃–SiO₂ ± H₂O ± CO₂ ± Na₂O     

Melting and Thermal Reconstitution of Pelitic Xenoliths, Wehr Volcano, East Eifel, West Germany

Pelitic xenoliths derived from amphibolite grade basement rocksoccur within a Pleistocene, trachytic, pyroclastic unit of theWehr volcano, East Eifel, West Germany: With increasing temperatureand/or prolonged heating at high temperature, quartz-plagioclaseand micaceous layers of the xenoliths have undergone meltingto form buchites and thermal reconstitution by dehydration reactions,melting and crystallization to form restites respectively. Thexenoliths provide detailed evidence of melting, high temperaturedecomposition of minerals, nucleation and growth of new phasesand P-T-f_o2 conditions of contact metamorphism of basement rocksby the Wehr magma. Melting begins at quartz-oligoclase (An_17·3Ab_82·3Or_0·4-An_20·0Ab_78·1Or_1·9)grain boundaries in quartz-plagioclase rich layers and the amountof melting is controlled by H₂O and alkalis released duringdehydroxylation/oxidation of associated micas. Initially, glasscompositions are heterogeneous, but with increasing degreesof melting they become more homogeneous and are similar to S-typegranitic minimum melts with SiO₂ between 71 and 77 wt. per cent;A/(CNK) ratios of 1·2–1·4; Na₂O < 2·95and normative corundum contents of 1·9–4·0per cent. Near micas plagioclase melts by preferential dissolutionof the NaAlSi₃O₈ component accompanied by a simultaneous increasein CaAl²Si²O⁸ (up to 20 mol. per cent An higher than the bulkplagioclase composition) at the melting edge. With increasingtemperature the end product of fractional melting is the formationand persistence of refractory bytownite (An_78–80) in thosexenoliths where extensive melting has taken place. Initial stage decomposition of muscovite involves dehydroxylation(H₂O and alkali loss). At higher temperatures muscovite breaksdown to mullite, sillimanite, corundum, sanidine and a peraluminousmelt. Mullite (40–43 mol. per cent SiO₂) and sillimanite(49 mol. per cent SiO₂) are Fe₂O₃ and TiO₂ rich (up to 6·1–0·84and 3·6–0·24 wt. per cent respectively).Al-rich mullite (up to 77 wt. per cent Al₂O₃) occurs with corundumwhich has high Fe₂O₃ and TiO₂ (up to 6·9 and 2·1wt. per cent respectively). Annealing at high temperatures andreducing conditions results in the exsolution of mullite fromsillimanite and ilmenite from corundum. Glass resulting fromthe melting of muscovite in the presence of quartz is peraluminous(A/(CNK) = 1·3) with SiO² contents of 66–69 percent and normative corundum of 4 per cent. Sanidine (An_1·9Ab_26·0Or_72·1-An_1·3Ab_15·9Or_82·9)crystallized from the melt. Dehydroxylation and oxidation of biotite results in a decreaseof K₂O from 8·6 to less than 1 wt. per cent and oxidetotals (less H₂O + contents) from 96·5 to 88·6,exsolution of Al-magnetite, and a decrease in the Fe/(Fe + Mg)ratio from 0·41 to 0·17. Partial melting of biotitein the presence of quartz/plagioclase to pleonaste, Al-Ti magnetite,sanidine(An_2·0Ab_34·9Or63·1) and melt takesplace at higher temperatures. Glass in the vicinity of meltedbiotite is pale brown and highly peraluminous (A/CNK = 2·1)with up to 6 wt. per cent MgO+FeO_{(total iroq)} and up to 10 percent normative corundum. Near liquidus biotite with higher Al₂O₃and TiO₂ than partially melted biotite crystallized from themelt. Ti-rich biotites (up to 6 wt. per cent TiO₂) occur withinthe restite layers of thermally reconstituted xenoliths. Meltingof Ti-rich biotite and sillimanite in contact with the siliceousmelt of the buchite parts of xenoliths resulted in the formationof cordierite (100 Mg/(Mg+Fe+Mn) = 76·5–69·4),Al-Ti magnetite and sanidine, and development of cordierite/quartzintergrowths into the buchite melt. Growth of sanidine enclosedrelic Ca-plagioclase to form patchy intergrowths in the restitelayers. Cordierite (100 Mg/(Mg+Fe+Mn) = 64–69), quartz,sillimanite, mullite, magnetite and ilmenite, crystallized fromthe peraluminous buchite melt. Green-brown spinels of the pleonaste-magnetite series have awide compositional variation of (mol. per cent) FeAl₂O₄—66·6–45·0;MgAl₂O₄—53·0–18·7; Fe₃O₄—6·9–28·1;MnAl₂O₄—1·2–1·5; Fe₂TiO₄—0·6–6·2.Rims are generally enriched in the Fe₃O₄ component as a resultof oxidation. Compositions of ilmenite and magnetite (single,homogeneous and composite grains) are highly variable and resultfrom varying degrees of high temperature oxidation that is associatedwith dehydroxylation of micas and melting. Oxidation mainlyresults in increasing Fe³⁺, Al and decreasing Ti⁴⁺, Fe²⁺ inilmenite, and increasing Fe²⁺, Ti⁴⁺ and decreasing Fe³⁺ in associatedmagnetite. A higher degree of oxidation is reached with exsolutionof rutile from ilmenite and formation of titanhematite and withexsolution of pleonaste from magnetite. Ti-Al rich magnetite(5·1–7·5 and 8·5–13·5wt. per cent respectively) and ilmenite crystallized from meltsin buchitic parts of the xenoliths. Chemical and mineralogic evidence indicates that even with extensivemelting the primary compositions of individual layers in thexenoliths remained unmodified. Apparently the xenoliths didnot remain long enough at high temperatures for desilicationand enrichment in Al₂O₃, TiO₂, FeO, Fe₂O₃, and MgO that resultsby removal of a ‘granitic’ melt, and/or by interactionwith the magma, to occur. T °C-f_o2 values calculated from unoxidized magnetite/ilmenitegive temperatures ranging from 615–710°C for contactmetamorphism and the beginning of melting, and between 873 and1054°C for the crystallization of oxides and mullite/sillimanitefrom high temperature peraluminous melts. f_o2 values of metamorphismand melting were between the Ni-NiO and Fe₂O₃-Fe₃O₄ buffer curves.The relative abundance of xenolith types, geophysical evidenceand contact metamorphic mineralogy indicates that the xenolithswere derived from depths corresponding to between 2–3kb P_load = P_fluid. The xenoliths were erupted during the latestphreatomagmatic eruption from the Wehr volcano which resultedin vesiculation of melts in partially molten xenoliths causingfragmentation and disorientation of solid restite layers.     

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.     

Granulite-Facies Metamorphism at Molodezhnaya Station, East Antarctica

Granulite-facies quartzofeldpathic gneisses metamorphosed 1000m.y. ago are exposed around Molodezhnaya Station (67°40'S,46°E) in East Antarctica. In addition to quartz, K-feldspar,and plagioclase, the fourteen samples studied in detail consistof the assemblages biotite-orthopyroxene-magnetite, biotite-garnet-orthopyroxene-ilmenite±magnetite, biotite-garnet ± ilmenite ± magnetite,biotite-garnet-sillimanite-ilmenite ± rutile, and biotite-garnet-cordierite-ilmenite-(sillimanite-rutile).Garnets are pyrope-almandine (13 to 34 mol per cent pyrope).Biotite (X_Fe = 0.33 to 0.57) is rich in TiO₂ (4 to 6.3 wt percent) and its Al₂O₃ content depends on the mineral assemblage.Orthopyroxene (X_Fe = 0.45 to 0.60) contains 1.5 to 3.0 weightper cent Al₂O₃. By and large, the minerals are chemically homogeneousand compositional variations are systematic, which indicatecrystallization under equilibrium conditions. On the basis ofthe compositions of coexisting garnet-biotite, garnet-cordierite,garnet-plagioclase (with sillimanite), and garnet-plagioclase-orthopyroxene,temperatures and pressures during the granulite-facies metamorphismare estimated to be 700°C ± 30°C and 5.5 ±1 kb. Water pressure apparently was significantly less thantotal pressure. Alteration during events following the granulite-facies metamorphismhas resulted in chemical zoning in garnet, in which grain edgesare more iron-rich than cores, heterogeneous biotite compositions,and anomalous trends involving MnO. Temperatures based on biotiteand garnet-edge compositions range from 410 to 580°C. Differences in the chemical potential (µ) of water andoxygen in the fluid phase can explain compositional variationsamong the three sillimanite-bearing samples and the relativelyiron-rich compositions of garnet and biotite associated withcordierite. Apparently, the water released by the formationof cordierite remained in the rock, forcing µH₂O to increaseas cordierite formed. Buffering of fluid phase composition bythe mineral assemblage suggests that water was not removed fromthe Molodezhnaya rocks by flushing with CO₂-rich fluids duringmetamorphism, a hypothesis evoked to explain ‘dry’mineral assemblages in other granulite-facies terrains.     

Dissolution of Quartz, Albite, and Orthoclase in H2O-Saturated Haplogranitic Melt at 800{degrees}C and 200 MPa: Diffusive Transport Properties of Granitic Melts at Crustal Anatectic Conditions

We have conducted experiments on dissolution of quartz, albite,orthoclase, and corundum into H₂O-saturated haplogranite meltat 800°C and 200 MPa over a duration of 120–1488 hwith the aim of ascertaining the diffusive transport propertiesof granitic melts at crustal anatectic temperatures. Cylindersof anhydrous starting glass and a single mineral phase (quartzor feldspar) were juxtaposed along flat and polished surfacesinside gold or platinum capsules with 10 wt % added H₂O. Concentrationprofiles in glass (quenched melt) perpendicular to the mineral–glassinterfaces and comparison with relevant phase diagrams suggestthat melts at the interface are saturated in the dissolvingphases after 384 h, and with longer durations the concentrationprofiles are controlled only by diffusion of components in themelt. The evolution of the concentration profiles with timeindicates that uncoupled diffusion in the melt takes place alongthe following four linearly independent directions in oxidecomposition space: SiO₂, Na₂O, and K₂O axes (Si-, Na-, and K-eigenvectors,respectively), and a direction between the Al₂O₃, Na₂O, andK₂O axes (Al-eigenvector), such that the Al/Na molar ratio isequal to that of the bulk melt and the Al/(Na + K) molar ratiois equal to the equilibrium ASI (= mol. Al₂O₃/[Na₂O + K₂O])of the melt. Experiments in which a glass cylinder was sandwichedbetween two mineral cylinders—quartz and albite, quartzand K-feldspar, or albite and corundum—tested the validityof the inferred directions of uncoupled diffusion and exploredlong-range chemical communication in the melt via chemical potentialgradients. The application of available solutions to the diffusionequations for the experimental quartz and feldspar dissolutiondata provides diffusivities along the directions of the Si-eigenvectorand Al-eigenvector of (2·0–2·8) x 10^–15m²/s and (0·6–2·4) x 10^–14 m²/s, respectively.Minimum diffusivities of alkalis [(3–9) x 10^–11m²/s] are orders of magnitude greater than the tetrahedral componentsof the melt. The information provided here determines the rateat which crustal anatexis can occur when sufficient heat issupplied and diffusion is the only mass transport (mixing) processin the melt. The calculated diffusivities imply that a quartzo-feldspathicsource rock with initial grain size of 2–3 mm undergoinghydrostatic, H₂O-saturated melting at 800°C (infinite heatsupply) could produce 20–30 vol. % of homogeneous meltin less than 1–10 years. Slower diffusion in H₂O-undersaturatedmelts will increase this time frame. KEY WORDS: chemical diffusion; haplogranite; mineral dissolution experiments; crustal anatexis     

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.     

The Effect of Reaction Overstep on Garnet Microtextures in Metapelitic Rocks of the Ilesha Schist Belt, SW Nigeria

Garnet-bearing assemblages of K-rich and K-poor metapelitesfrom the Ilesha Schist belt, SW Nigeria, are investigated. K-richsamples contain the assemblages (A) garnet–staurolite–muscovite–chlorite–magnetite,(B) andalusite–garnet–staurolite–muscovite–chlorite–magnetiteand (C) sillimanite–andalusite–garnet–muscovite–chlorite–magnetite.K-poor samples contain the assemblages (D) garnet–staurolite–cordierite–chloriteand (E) garnet–cordierite–chlorite ± staurolite.All assemblages contain quartz, plagioclase, biotite and ilmenite.P–T pseudosections calculated in the system CaO–Na₂O–K₂O–TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂ –H₂O ± O₂ suggest peak metamorphismat 590 ± 20°C at 5 ± 0·5 kbar, followedby retrogression to 550°C at 3·0 kbar, in agreementwith field evidence, domain assemblages, mineral compositions,modes and geothermobarometry. The absence of compositional zonationshows that garnet in all investigated rocks nucleated and grewat constant P–T–X in equilibrium with associatedminerals on the thin-section scale. However, the garnet-in reactiondid not begin until the establishment of a significant temperatureoverstep of     

Volcan Popocatepetl, Mexico. Petrology, Magma Mixing, and Immediate Sources of Volatiles for the 1994-Present Eruption

Volcán Popocatépetl has been the site of voluminousdegassing accompanied by minor eruptive activity from late 1994until the time of writing (August 2002). This contribution presentspetrological investigations of magma erupted in 1997 and 1998,including major-element and volatile (S, Cl, F, and H₂O) datafrom glass inclusions and matrix glasses. Magma erupted fromPopocatépetl is a mixture of dacite (65 wt % SiO₂, two-pyroxenes+ plagioclase + Fe–Ti oxides + apatite, 3 wt % H₂O, P= 1·5 kbar, f_O2 = NNO + 0·5 log units) and basalticandesite (53 wt % SiO₂, olivine + two-pyroxenes, 3 wt % H₂O,P = 1–4 kbar). Magma mixed at 4–6 km depth in proportionsbetween 45:55 and 85:15 wt % silicic:mafic magma. The pre-eruptivevolatile content of the basaltic andesite is 1980 ppm S, 1060ppm Cl, 950 ppm F, and 3·3 wt % H₂O. The pre-eruptivevolatile content of the dacite is 130 ± 50 ppm S, 880± 70 ppm Cl, 570 ± 100 ppm F, and 2·9 ±0·2 wt % H₂O. Degassing from 0·031 km³ of eruptedmagma accounts for only 0·7 wt % of the observed SO₂emission. Circulation of magma in the volcanic conduit in thepresence of a modest bubble phase is a possible mechanism toexplain the high rates of degassing and limited magma productionat Popocatépetl. KEY WORDS: glass inclusions; igneous petrology; Mexico; Popocatépetl; volatiles     

Low-temperature Compatibility Relations of Cordierite in Haplopelites of the System K2O--MgO--Al2O3--SiO2--H2O

The equilibrium temperatures of the reaction muscovite+chlorite+quartz= cordierite+phlogopite+H₂O (1) in the pure system K₂O—MgO—Al₂O₂—SiO₂—H₂Owere found to be 495±10°C at 1 kb P_H2O; 525±10°Cat 2 kb; 610±15°C at 5 kb; 635±10°C at6 kb. From intersection of this curve with the lower temperaturestability limit of cordierite close to 645°C, 6.5 kb P_H2O,a reaction cordieritc+muscovite = phlogopite+aluminum silicate+quartz+H₂O(2) is generated which has a negative slope and passes throughthe points 645°C, 6.5 kb PH₂O and 700°C, 5 kb PH₂O.On the high-pressure side of this reaction curve cordieriteis restricted to K₂O—poor bulk compositions. Application of the experimentally determined phase relationsto more complex natural pelitic rocks suggests that reaction(1) represents maximum temperatures for the disappearance ofchlorite from pelitic assemblages containing muscovite and quartz,whereas reaction (2) gives maximum water pressures for the disappearanceof cordierite from these rocks.     

The Substitution of Al and F in Titanite at High Pressure and Temperature: Experimental Constraints on Phase Relations and Solid Solution Properties

Experimental studies were carried out to evaluate phase relationsinvolving titanite–F–Al-titanite solid solutionin the system CaSiO₃–Al₂SiO₅–TiO₂–CaF₂. Theexperiments were conducted at 900–1000°C and 1·1–4·0GPa. The average F/Al ratio in titanite solid solution in theexperimental run products is 1·01 ± 0·06,and X_Al ranges from 0·33 ± 0·02 to 0·91± 0·05, consistent with the substitution [TiO²⁺]_–1[AlF²⁺]₁.Analysis of the phase relations indicates that titanite solidsolutions coexisting with rutile are always low in X_Al, whereasthe maximum X_Al of titanite solid solution occurs with fluoriteand either anorthite or Al₂SiO₅. Reaction displacement experimentswere performed by adding fluorite to the assemblage anorthite+ rutile = titanite + kyanite. The reaction shifts from 1·60GPa to 1·15 ± 0·05 GPa at 900°C, from1·79 GPa to 1·375 ± 0·025 GPa at1000°C, and from 1·98 GPa to 1·575 ±0·025 GPa at 1100°C. The data show that the activityof CaTiSiO₄O is very close to the ideal molecular activity model(X_Ti) at 1100°C, but shows a negative deviation at 1000°Cand 900°C. The results constrain     

The Formation of Chrysoberyl in Metamorphosed Pegmatites

Mineral assemblages in pegmatite samples from Kolsva, Swedenand Marikov, Czechoslovakia show that chrysoberyl is alwaysaccompanied by quartz, and is a breakdown product of primarypegmatitic beryl. Textures and the mineral-forming process forthe Kolsva pegmatite are explained by the reactions beryl +K-feldspar + H+ = chrysoberyl + quartz + SiO_{2, aq} + K⁺ + H₂Oor alternatively beryl —K—feldspar + H₂O = chrysoberyl+ quartz + melt. Mineral assemblages from mica-rich parts ofthe pegmatite include sillimanite—K—feldspar, muscovite—K—feldspar—sillimanite,and annite—magnetite—spinel—sillimanite—garnet.Details about the composition and the textural relationshipsof these minerals are given; they indicate a post-pegmatiticmetamorphic event at P—T conditions near to the anatecticregime. The samples from Marikov show textures, which are explainedby the reactions beryl + albite + H⁺ = chrysoberyl + quartz+ Na⁺ + H₂O or alternatively beryl + albite + H₂O = chrysoberyl+ quartz + melt. Breakdown of muscovite produces sillimaniteaccording to the reactions beryl + albite + muscovite + H⁺ =chrysoberyl + quartz + sillimanite + Na⁺ + K⁺ + H₂O or alternativelyberyl + albite + muscovite + H₂O = chrysoberyl + quartz + sillimanite+ melt. Similar reaction textures and mineral assemblages were foundin other chrysoberyl-bearing pegmatites (Maroankora, Madagascar;Helsinki, Finland; Haddam, Greenfield, Greenwood, U.S.A.). Hydrothermal experiments located the reaction beryl + alkalifeldspar + H₂O = chrysoberyl + phenakite + melt at P—Tconditions between the K—feldspar—quartz—H₂Osolidus and the K—feldspar—albite—quartz-H₂Osolidus. It is concluded that the formation of Al-rich minerals likechrysoberyl and sillimanite in pegmatites is due to a post-pegmatiticevent at high P—T conditions. The question as to whichof the alternative set of reactions is more likely, the ionicequilibria or the anatectic chrysoberyl formation, must be leftopen. The previous hypothesis of a desilification of a pegmatitewhich intruded into SiO₂-poor country rocks, or of the assimilationof Al₂O₃-rich country rocks, cannot explain the mineral assemblagesof the two pegmatites.     

A 2.5 ka History of Dacitic Magmatism at Nevado de Toluca, Mexico: Petrological, 40Ar/39Ar Dating, and Experimental Constraints on Petrogenesis

After 11·5 ka of quiescence (24·5–13 ka),the Nevado de Toluca volcano started a 2500 year period of activity.This period was characterized by a dome destruction event at13 ka, a small Plinian event at 12·1 ka, and a largePlinian eruption at 10·5 ka. About 10 km³ of magma waserupted that was homogeneous in composition (63·3–65·7SiO₂ wt % whole-rock) and in mineralogy. Pumice consists ofplagioclase (An_30–59) > orthopyroxene (En_56–59)> hornblende >> Fe–Ti oxides + rare apatite (inopx) + biotite, set in a rhyolitic matrix (72–76 SiO₂wt %). ⁴⁰Ar/³⁹Ar analysis of single biotite crystals yieldedages (0·81–4·7 Ma), that do not correspondto eruption ages. The biotite represents partially assimilatedxenocrysts, which could have resided in the magma for only ashort period of time. Mineral chemical data, coupled with hydrothermalexperiments, indicate that prior to eruption the dacitic magmastagnated at a depth of 4·5–6 km below the summitat water pressures of 160–210 MPa and a temperature of824 ± 12°C on the basis of Fe–Ti oxide thermometry,and under water-saturated conditions. To stabilize a homogeneousmagma body of >10 km³ at 824°C in the upper crust, wepropose that reheating of the dacitic reservoir by hotter magmabatches was able to maintain the equilibrium between the temperatureof the magma and the assimilation of wall-rock over a periodof 2500 years. Based on similarities among the juvenile products,we suggest that the three eruptions were fed from the same magmabody. KEY WORDS: explosive volcanism; xenocrystic contamination; Nevado de Toluca, Mexico     

A Biotite Isograd in South-Central Maine, U.S.A.: Mineral Reactions, Fluid Transfer, and Heat Transfer

The biotite isograd in pelitic schists of the Waterville Formationinvolved reaction of muscovite + ankerite + rutile + pyrite+graphite + siderite or calcite to form biotite + plagioclase+ ilmenite. There was no single reaction in all pelites; eachrock experienced a unique reaction depending on the mineralogyand proportions of minerals in the chlorite-zone equivalentfrom which it evolved. Quartz, chlorite, and pyrrhotite werereactants in some rocks and products in others. All inferredbiotite-forming reactions involved decarbonation and desulfidation;some were dehydration reactions and others were hydration reactions.P-T conditions at the biotite isograd were near 3500 bars and400 °C. C-O-H-S fluids in equilibrium with the pelitic rockswere close to binary CO₂-H₂O mixtures with X_CO2 = 0.02–0.04.During the biotite-forming reaction, pelitic rocks (a) decreasedby 2–5 percent in volume, (b) performed – (4–11)kcal/liter P-V work on their surroundings, (c) absorbed 38–85kcal/liter heat from their surroundings, and (d) were infiltratedby at least 0.9–2.2 rock volumes H₂O fluid. The biotite isograd sharply marks the limit of a decarbonationfront that passed through the terrane during regional metamorphism.Decarbonation converted meta-shales with 6–10 per centcarbonate to carbonate-free pelitic schists. One essential causeof the decarbonation event was pervasive infiltration of theterrane by at least 1–2 rock volumes H₂O fluid early inthe metamorphic event under P-T conditions of the biotite isograd.Average shale contains 4–13 per cent siderite, ankerite,and/or calcite, but average pelitic schist is devoid of carbonateminerals. If the Waterville Formation serves as a general modelfor the metamorphism of pelitic rocks, it is likely that worldwidemany pelitic schists developed by decarbonation of shale caused,in part, by pervasive infiltration of metamorphic terranes byseveral rock volumes of aqueous fluid during an early stageof the metamorphic event.     

P--T Stabilities of Laumontite, Wairakite, Lawsonite, and Related Minerals in the System CaAl2Si2O8-SiO2-H2O

Hydrothermal investigation of the bulk composition CaO.Al₂O₃.4SiO₂+excessH₂O has been conducted using conventional techniques over thetemperature ranges 200–450 °C and 500–6000 barsP_fluid. A number of reactions have been studied by employingmineral mixtures consisting of reactants and products in about9: 1 and 1: 9 ratios. The phase relations were deduced fromrelatively long experiments by observing which seeded assemblagedisappeared or decreased markedly in one of the paired run charges. Laumontite was synthesized in the laboratory, probably for thefirst time. Laumontite was grown from seeded wairakite to over99 per cent using a weak NaCl solution. The refractive indicesof the synthetic material are about = 1.504 and = 1.514. Theaverage unit cell dimensions are a₀ = 14.761±0.005 Å;b₀ = 13.077±0.005 Å; c₀ = 7.561±0.003 Å;and ß = 112.02°±0.04°. Within the errorof measurement, the optical properties and cell parameters arein good agreement with those of natural laumontite. The equilibriumdehydration of laumontite involves two reactions: (1) laumontite= wairakite+2H₂O, passing through about 230 °C at 0.5 kb,255±5 °C at 1 kb, 282±5 °C at 2 kb, 297±5°C at 3 kb and 325±5 °C at 6 kb; and (2) laumontite= lawsonite+2 quartz+2H₂O, taking place at about 210 °Cat 3 kb and 275 °C at 3.2 kb. Above 300 °C, the equilibriumcurve for the solid-solid reaction (3) lawsonite+2 quartz =wairakite passes through 305 °C, 3.4 kb and 390 °C,4.4 kb. Equilibrium has been demonstrated unambiguously forthe above three reactions. The hydrothermal decomposition ofnatural laumontite above its own stability limit appears tobe a very slow process. Combined with previously published equilibria determined hydrothermallyfor wairakite, the phase relations are further investigatedby chemographic analysis interrelating the phases, laumontite,wairakite, lawsonite, anorthite, prehnite+kaolinite, and 2 pumpellyite+kaolinitein the system CaAl₂Si₂O₈-SiO₂-H₂O. This synthesis allowed theconstruction of a semiquantitative petrogenetic grid applicableto natural parageneses and the delineation of the physical conditionsfor the various low-grade metamorphic facies in low µCO₂environments. The similar stratigraphic zonations, consistentlyfound in a variety of environments, are recognized to be a functionof burial depth, geothermal gradient, and mineralogical andchemical composition of the parental rocks. Departures fromthe normal sequences are believed to be due to the combinationsof mineralogical variations, availability of H₂O, differencesin the ratio µCO₂/µH₂O, and the rate of reaction.The possible P-T boundaries for diagenesis, the zeolite facies,the lawsonite-albite facies, the prehnite-pumpellyite facies,and the adjacent metamorphic facies are illustrated diagrammatically.     

Experimental Interaction of Granitic and Basaltic Magmas and Implications for Mafic Enclaves

We have performed time series experiments for periods rangingfrom 3 min to 44 h on the interaction of granite melt and partiallymolten basalt at 920C and 10 kbar, in the presence of 5 wt.%water. With time, the assemblage of the basalt domain changesfrom predominantly amphibole+plagioclase to clinopyroxene+garnet;the melt fraction increases from {small tilde}2•5 to 40%;and between the two domains, the melt compositions progressivelyequilibrate. Initially in each run, melts of the basalt domainhave uniform plateau concentrations for SiO₂, Al₂O₃, CaO, MgO,and FeO because the activities of these components are regulatedby the mineral assemblage, but at advanced stages of reaction,no such control is evident. We have derived analytical expressionsto describe and simulate the diffusion profiles. The concentrationprofiles for SiO₂, Al₂O₃, CaO, and Na₂O in the granite, emanatingfrom the basalt–granite interface, have been used to estimateeffective diffusivities. The values from the shorter runs arecompared with those of the experiment of longest duration forwhich we assumed finite couples in our calculations. In thediffusion calculations for K₂O the difference in melt fractionbetween the two domains is accounted for. The resulting values(in cm²/s) are: D_Na2O=6 10^–7, D_K2O=3 10^–7, D_MgO=9 10^–8, D_CaO=(4–6) 10^–8, and D_SiO2 and D_Al2O3=(3–0•6) 10^–8. They are in reasonable agreement with values fromother studies. On the basis of our experiments we calculatethat mafic enclaves of magmatic origin should equilibrate toa large degree with their host magma in slowly cooling non-convectinggranitic plutons. Enclaves approaching complete re-equilibrationretain distinctly higher modal amounts of mafic minerals. Theydo not compositionally resemble binary magma mixtures, but aremore like host magma with accumulated crystals. We show thatthe modal differences between enclave and host are indicativeof the temperature of homogenization and that, in principle,this temperature can be deduced from equilibrium phase diagrams. ^* Present address: Mineralogisch-Petrologisches Institut, Universitt Gttingen, Goldschmidtstrasse 1, 3400 Gttingen, Germany     

Magmatic Evolution of the La Pacana Caldera System, Central Andes, Chile: Compositional Variation of Two Cogenetic, Large-Volume Felsic Ignimbrites

La Pacana is one of the largest known calderas on Earth, andis the source of at least two major ignimbrite eruptions witha combined volume of some 2700 km³. These ignimbrites have stronglycontrasting compositions, raising the question of whether theyare genetically related. The Toconao ignimbrite is crystal poor,and contains rhyolitic (76–77 wt % SiO₂) tube pumices.The overlying Atana ignimbrite is a homogeneous tuff whose pumiceis dacitic (66–70 wt % SiO₂), dense (40–60% vesicularity)and crystal rich (30–40 % crystals). Phase equilibriaindicate that the Atana magma equilibrated at temperatures of770–790°C with melt water contents of 3·1–4·4wt %. The pre-eruptive Toconao magma was cooler (730–750°C)and its melt more water rich (6·3–6·8 wt% H₂O). A pressure of 200 MPa is inferred from mineral barometryfor the Atana magma chamber. Isotope compositions are variablebut overlapping for both units (⁸⁷Sr/⁸⁶Sr_i 0·7094–0·7131;¹⁴³Nd/¹⁴⁴Nd 0·51222–0·51230) and are consistentwith a dominantly crustal origin. Glass analyses from Atanapumices are similar in composition to those in Toconao tubepumices, demonstrating that the Toconao magma could representa differentiated melt of the Atana magma. Fractional crystallizationmodelling suggests that the Toconao magma can be produced by30% crystallization of the observed Atana mineral phases. Toconaomelt characteristics and intensive parameters are consistentwith a volatile oversaturation-driven eruption. However, thelow H₂O content, high viscosity and high crystal content ofthe Atana magma imply an external eruption trigger. KEY WORDS: Central Andes; crystal-rich dacite; eruption trigger; high-silica rhyolite; zoned magma chamber