Oxygen and Hydrogen Isotope Geochemistry of the Mourne Mountains Tertiary Granites, Northern Ireland

An oxygen and hydrogen isotopic study of minerals and wholerocks from the granites of the Mourne Mountains Tertiary complex,and related rocks, shows that whereas a significant circulationof meteoric water was associated with the complex, it had onlyminor and localized effects on the granites themselves. TheSilurian slate and greywacke country rocks, which would havehad ¹⁸O_(SMOW) values of +10 to +20 before the Tertiary igneousevents, have been depicted ¹⁸O to values of –40 to –05Tertiary acid minor intrusions outside the main granite massesare also ¹⁸O depleted. ^l8O whole-rock data on the granites showa range of +6.0 to +9.5, and include values significantly higherthan most of those obtained for the granites of the Tertiarycentral complexes of Skye, Mull, and Ardnamurchan. Many of thelowest whole-rock ¹⁸O values are found in samples where theminerals are not in isotopic equilibrium. The mineral oxygenisotopic data can be explained in terms of localized interactionwith meteoric water, resulting in preferential ¹⁸O depletionin feldspar(s) and biotite, with quartz being much less affected.The granites all show low values of D_(SMOW) for biotite andamphibole separates (–137 to –104). The lowest valuesoccur close to the margins of the plutons, near internal contactsor near greisen localities, and these probably reflect limitedinteraction with meteoric water. The higher D values are fromsamples which show evidence of chloritization. This processappears to have occurred both during interaction with meteoricwater, and also during autometasomatism by an exsolved magmaticfluid in other parts of the plutons, including central locationswhere there is little or no evidence for the penetration ofmeteoric water. Granite samples which exhibit near-equilibriumoxygen isotope fractionations for constituent minerals are characterizedby magmatic O-isotopic compositions. The G2 granite, the largestpluton of the eastern centre, has a magmatic ¹⁸O_(SMOW) valueof {small tilde}+95; intrusions G3 (eastern centre) and G4(western centre) both have ¹⁸O_(SMOW) values of {small tilde}+90.The other two main intrusive phases have distinctly lower ¹⁸O_(SMOW)values: {small tilde}+75 for Gl (the least fractionated graniteof the Mourne Mountains central complex), and from +75 to +85for G5. The oxygen isotopic data rule out simple partial meltingof the country rocks as the origin of the granites and alsopreclude an origin by closed-system fractional crystallizationof basaltic magma typical of that represented by Tertiary basicigneous rocks of the region. ^* Present address: NERC Isotope Geosciences Laboratory, Keyworth, Nottingham BG12 5GG, UK Present address: School of Engineering Technology, Georgian College, Barrie, Ontario, L4M 3X9, Canada     

The Ni-S System and Related Minerals

The system Ni-S has been studied systematically from 200^? to1, 030^? C by means of evacuated, sealed silica-glass tube experimentsand differential thermal analyses. Compounds in the system areNi₃S₂ (and a high temperature, non-quenchable Ni_3?S₂ phase),Ni₇S₆, Ni₁–S₄ Ni₃S₄, and NiS₂. The geologic occurrenceof the minerals heazlewoodite (Ni₂S₂), millerite (ßSNi₁-₂S),polydymite (Ni₃S₄), and vaesite (NiS₂) can now be describedin terms of the stability ranges of their synthetic equivalents. Hexagonal heazlewoodite, which is stoichiometric within thelimit of error of the experiments, inverts on heating to a tetragonalor pseudotetragonal phase at 556^? C. This high-temperature phase(Ni₃ has a wide field of stability, from 23.5 to 30.5 wt percent sulfur at 600^? C, and melts incongruently at 806^??3^? C.The ßNi₇S₆ phase inverts to Ni₇₈ at 397^? C6 when inequilibrium with Ni₃S₂, and at 400^? C when in equilibrium withNiS. Crystals of Ni₇S₆ break down to Ni₃-S₂+NiS at 573^??3^?C.The low-temperature form of Ni₁-S₁ corresponding to the mineralmillerite, is rhombohedral, and the high-temperature form hasthe hexagonal NiAs structure. Stoichiometric NiS inverts at379^??3^?C, whereas Ni₁-S with the maximum nickel deficiency invertsat 282^??5OC. The Ni₁-alphS-NiS₂ solvus was determined to 985^??3^?C,the eutectic temperature of these phases. Stoichiometric NiSis stable at 600^?C but breaks down to Ni₂-S₂ and Ni₁-S below797^?C, whereas Ni₁-S with 38.2 wt per cent sulfur melts congruentlyat 992^??3^?C. Vaesite does not vary measurably from stoichiometricNiS₂ composition, and melts congruently at 1.007?5^?C. Polydymitebreaks down to aNi-S? vaesite at 356^??3^?C. Differential thermalanalyses showed the existence of a two-liquid field in the sulfur-richportion of the system above 991^?C and over a wide compositionalrange.     

The Solubility of Alumina in Orthopyroxene Coexisting with Garnet in FeO-MgO--Al2O3--SiO2 and CaO--FeO--MgO--Al2O3--SiO2

The pressure-temperature-compositional (P-T-X) dependence ofthe solubility of Al₂O₃ in orthopyroxene coexisting with garnethas been experimentally determined in the P-T range 5–30kilobars and 800–1200 ?C in the system FeO—MgO—Al₂O₃—SiO₂(FMAS). These results have been extended into the CaO—FeO—MgO—Al₂O₃—SiO₂(CFMAS) system in a further set of experiments designed to determinethe effect of the calcium content of garnet on the Al₂O₃ contentsof coexisting orthopyroxene at near-constant Mg/(Mg + Fe). Startingmaterials were mainly glasses of differing Mg/(Mg + Fe) or Ca/(Ca+ Mg + Fe) values, seeded with garnet and orthopyroxene of knowncomposition, but mineral mixes were also used to demonstratereversible equilibrium. Experiments were performed in a piston-cylinderapparatus using a talc/pyrex medium. Measured orthopyroxene and corrected garnet compositions werefitted by multiple and stepwise regression techniques to anequilibrium relation in the FMAS system, yielding best-fit,model-dependent parameters G^o_y= –5436 + 2.45T cal mol^–1,and W^M1_FeA1= –920 cal mol^–1. The volume change ofreaction, V^o, the entropy change, S^o₉₇₀ and the enthalpy changeH^o_1,970, were calculated from the MAS system data of Perkinset al. (1981) and available heat capacity data for the phases.Data from CFMAS experiments were fitted to an expanded equilibriumrelation to give an estimate of the term W^ga_CaMg = 1900 ? 400cal/mole cation, using the other parametric values already obtainedin FMAS. The experimental data allow the development of a arnet-orthopyroxenegeobarometer applicable in FMAS and CFMAS: where This geobarometer is applicable to both pelitic and metabasicgranulites containing garnet orthopyroxene, and to garnet peridoditeand garnet pyroxenite assemblages found as xenoliths in diatremesor in peridotite massifs. It is limited, however, by the necessityof an independent temperature estimate, by errors associatedwith analysis of low Al₂O₃ contents in orthopyroxenes in high-pressureor low-temperature parageneses, and by uncertainties in thecomposition of garnet in equilibrium with orthopyroxene. Ananalysis of errors associated with this formulation of the geobarometersuggests that it is subject to great uncertainty at low pressuresand for Fe-rich compositions. The results of application ofthis geobarometer to natural assemblages are presented in acompanion paper.     

A New Interpretation of Centimetre-scale Variations in the Progress of Infiltration-driven Metamorphic Reactions: Case Study of Carbonated Metaperidotite, Val d'Efra, Central Alps, Switzerland

Progress () of the infiltration-driven reaction, 4olivine +5CO₂ + H₂O = talc + 5magnesite, that occurred during Barrovianregional metamorphism, varies at the cm-scale by a factor of3·5 within an 3 m³ volume of rock. Mineral and stableisotope compositions record that X_CO2, ¹⁸O_fluid, and ¹³C_fluidwere uniform within error of measurement in the same rock volume.The conventional interpretation of small-scale variations in in terms of channelized fluid flow cannot explain the uniformityin fluid composition. Small-scale variations in resulted insteadbecause (a) reactant olivine was a solid solution, (b) initiallythere were small-scale variations in the amount and compositionof olivine, and (c) fluid composition was completely homogenizedover the same scale by diffusion–dispersion during infiltrationand subsequent reaction. Assuming isochemical reaction, spatialvariations in image variations in the (Mg + Fe)/Si of the parentrock rather than the geometry of metamorphic fluid flow. Ifinfiltration-driven reactions involve minerals fixed in composition,on the other hand, spatial variations in do directly imagefluid flow paths. The geometry of fluid flow can never be determinedfrom geochemical tracers over a distance smaller than the oneover which fluid composition is completely homogenized by diffusion–dispersion. KEY WORDS: Alpine Barrovian metamorphism; diffusion; metamorphic fluid composition; metamorphic fluid flow; reaction progress     

Dehydration--Melting Phenomena in Leptynitic Gneisses and the Generation of Leucogranites: a Case Study from the Kerala Khondalite Belt, Southern India

Pan-African high-grade metamorphism in the Kerala KhondaliteBelt (South India) led to the in situ formation of garnet-bearingleucosomes (L1) in sodic quartz—alkali feldspar—biotitegneisses. Microtextures, mineralogy and the geochemical characteristicsof in situ leucosomes (L1) and gneiss domains (GnD) indicatethat the development of leucosomes was mainly controlled bythe growth of garnet at the expense of biotite. This is documentedby the selective transfer of FeO, MgO, , Sm and the heavy rareearth elements into the L1 domains. P-T constraints (T>800C,P>6kbar, aH₂O0.3) suggest that the leucosomes were formedthrough complete melting of biotite in fluid-absent conditions,following the model reaction Biotite+Alkali feldspar+QuartzlGarnet+Ilmenite+Melt.The fraction of melt generated during this process was low (<10vol.%). The identical size of the leucosomes as well as theirhomogeneous and isotropic distribution at outcrop scale, whichlacks any evidence for melt segregation, suggest that the migmatiteremained a closed system. Subsequent to migmatization, the leptyniticgneisses were intruded by garnet-bearing leucogranitic melts(L2), forming veins parallel and subperpendicular to the foliation.The leucogranites are rich in potassium (K₂O5.5 wt%), (Ba400p.p.m.) and Sr (300 p.p.m.), and exhibit low concentrationsof Zr (40 p.p.m.), Th (<1 p.p.m.) and (<10 p.p.m.). Thechondrite-normalized REE spectra show low abundances (La_N20,Lu_N3) and are moderately fractionated (La_N/Lu_N7). An Eu anomalyis absent or weakly negative. The higher ⁸⁷Sr/⁸⁶Sr ratio at550 Ma (0.7345) compared with the migmatite (0.7164) precludesa direct genetic relationship between leptynitic gneisses andleucogranites at Manali.Nevertheless, the chemical and mineralogicalcompositions of the leuocogranites strongly favour a derivationthrough fluid-absent biotite melting of isotopically distinctbut chemically comparable Manali-type gneisses. The undersaturationof Zr, Th and REE, a typical feature of leucogranitic meltsgenerated during granulite facies anatexis of psammo-peliticlithologies and attributed to disequilibrium melting with incompletedissolution of accessory phases (zircon, monazite), is weaklydeveloped in the leucogranites of Manali.It is concluded thatthis is mainly due to the sluggish migration of the melts instatic conditions, which facilitated equilibration with therestitic gneisses. ^*Fax: 0228-732763; e-mail: ingo.braun{at}uni-bonn.de     

Fluid--Rock Interaction during Low-Pressure Polymetamorphism of the Reynolds Range Group, Central Australia

Marbles and metapelites from the Reynolds Range Group (centralAustralia) were regionally metamorphosed at low pressure duringM₂ at 1.6 Ga, M₂ ranged in grade from greenschist to granulitefacies along the length of the Reynolds Range, and overprinted1.78 Ga granites and their contact aureoles in the ReynoldsRange Group metasediments. At all M₂ grades the marbles andmetapelites have highly variable oxygen isotope ratios [marbles:¹⁸O(carb) 14–20%; metapelites: ¹⁸O 6–14%). Similarly, 1.78 Ga granites have highly variable oxygen isotope ratios(¹⁸O 5–13%), with the lowest values occurring at thegranite margins. In all rock types, the lowest oxygen isotopevalues are consistent with the infiltration of channelled magmaticand/or meteoric fluids. The variable lowering of oxygen isotopevalues resulted from pre-M₂ contact metamorphism and fluid—rockinteraction around the 1.78 Ga granites. In contrast, mineralassemblages in the marbles define a trend of increasing X_CO2with increasing grade from <0.05 (greenschist facies) to0.7–1.0 (granulite facies). This, together with the lackof regionally systematic resetting of oxygen isotope ratios,implies that there was little fluid—rock interaction duringprograde regional metamorphism. KEY WORDS: low pressure; polymetamorphism; fluids; stable isotopes; petrology ^*Corresponding author Fax: 61–3–94791272. e-mail: geoisb{at}lure.latrobe.edu.au     

(Ruby--Sapphire)--Chromian Mica--Tourmaline Rocks from Westland, New Zealand

Boulders of the assemblage ruby—sapphire corundum, chromianmuscovite, margarite, tourmaline (chromian chlorite, Zn—Mnchromite and Mn—Ti magnetite) occur in glacial moraineand rivers of north Westland, South Island of New Zealand. Thelocation, Cr-rich composition of the boulders and the presenceof rare serpentinite rinds indicate that they are derived fromultramafic rocks (Pounamu Ultramafics) that occur within AlpineSchist of the Southern Alps. The largest sample is progressivelyzoned outwards from a corundum—margarite core, throughan intermediate zone of Cr-muscovite, to an outer zone of Cr-chloritethat is in contact with serpentinite. Most finds consist oferosion-resistant corundum-rich cores. In the corundum, Cr₂O₃content ranges from 0.5 to 13%, with red coloration becomingmore intense with increasing Cr. In addition to the dominantCr³⁺ Al³⁺ substitution, those of (Fe, V)³⁺ Cr³⁺ and (Ti⁴⁺+Fe²⁺) 2Cr³⁺ result in spectacular colour zoning from colourlessto deep ruby red-carmine and pale blue to dark blue—violet.Corundum has grown by replacement of the micaceous matrix thatconsists of chromian muscovite (0.10–4.10% Cr₂O₃) andchromian margarite (0.46–1.20% Cr₂O₃). Both micas containa significant paragonite component (up to 21.5% in muscoviteand up to 40.8% in margarite). Late phase muscovite is Ba richwith up to 4.77% BaO, and margarite has up to 0.66% SrO. Tourmalineoccurs as veins, vein outgrowths and larger poikilitic crystalsthat replace the mica matrix. Chromium content ranges between0.82 and 3.6% Cr₂O₃. High bulk rock Al (up to 78% Al₂O₃), K,Ca, Cr and Na, and low Si (14.5–23.1% SiO₂), suggest thatthe corundum—Cr-silicate rocks are the products of extrememetasomatic alteration of quartzofeldspathic schist enclavesin serpentinite. Isocon analysis indicates that conversion ofthe schist to the micaceous matrix of the corundum rocks involvesconservation of Ca, Al, K, volatiles and Sr, a mass loss of59% and a volume reduction of 69% consequent on removal of 70–80%Si and all other elements (most >80%), with enrichment ofbetween 900 and 1800% Cr. The formation of corundum from themica matrix involved a further mass—volume reduction anddecrements in Si, Ca, K, volatiles and Sr from reaction sites.Concentric mineral zonation in single rock samples and zoning—replacementin minerals, e.g. Cr in corundum and chromite, Ti, Fe²⁺ in corundum,Ba in muscovite, Sr in margarite, and Mn and Zn in chromiteand magnetite, imply element redistribution during metasomatism.Experimental reaction between quartzofeldspathic schist andserpentinite at 450C and 2 kbar produced reaction sequencescontaining newly formed Ca-plagioclase—phlogopitic micachloriteand muscovite—chlorite that in terms of composition areanalogous with the observed (corundum—margarite)—muscovite—chloritezonation. The temperature of metamorphism of garnet zone rocks(45020C) that contain the corundum—Cr-silicate rocksis well below that of the breakdown of muscovite and margariteto form corundum and indicates the importance of fluid composition,particularly the cation—hydrogen variables a_Ca²⁺/H⁺, aK⁺/H₊and a_S1O2. Introduction of boron into the schist (from serpentinite),and boron released from the breakdown of original tourmalinein the schist, resulted in tourmaline veining and reaction ofthe mica matrix to form tourmaline that invoved both a massand volume increase and addition of Fe, Mg together with B. KEY WORDS: corundum—Cr-silicate rocks; metasomatism; New Zealand; Southern Alps ^*Corresponding author.     

Rock-buffered Fluid Evolution of Metapelites and Quartzites in the Picuris Range, Northern New Mexico

Pelitic schists and quartzites in the Picuris Range of northernNew Mexico exhibit mineral ¹⁸O and D compositions that indicaterock-buffered isotopic exchange during metamorphism at uniformphysical conditions of T 530C and P 4 kbar. Phase assemblagesand major-element compositions among silicates and oxides areuniform within stratigraphic units, but they change abruptlyacross lithologic contacts, yielding distinctive mineral Mg/Fe²⁺ratios and inferred f(O₂) values. Mineral compositions reflectthe pre-metamorphic compositions of individual rock units. O-and H-isotopic compositions of quartz and muscovite are alsodiscontinuous across lithologic boundaries, showing intra-layerhomogeneity and bulk-rock isotopic compositions retained fromsedimentary protoliths. Uniform ¹⁸ O_Qu-Ms values indicate isotopicequilibrium at peak metamorphic conditions. Sharp discontinuitiesin mineral and fluid isotopic compositions reflect limited isotopicexchange between units. The isotopic system in these units wasprobably one of rock-buffered exchange, in which the sedimentarycompositions of individual rock units exerted the dominant controlon mineral and fluid isotopic composition over short distancesin a relatively closed metamorphic system. Fluid migration duringprogressive metamorphic devolatilization in this simple systemwas probably non-pervasive, and it was probably influenced bycontrasting rock permeability. Consequently, our study suggeststhat pervasive exchange between interlayered units may be uncommonin regionally metamorphosed terrains that show weak initialgeochemical gradients. In contrast, the chemical and isotopichomogenization that attends pervasive fluid flow and high fluidfluxes may be restricted to settings characterized by extremegeochemical gradients, such as interlayered silicates and carbonates,or terrains that host plutonic hydrothermal systems. KEY WORDS: fluids; metamorphism; stable isotopes; New Mexico ^*Corresponding author. E-mail: jgoodgc{at}sun.cis.smu.edu.. Telephone (214) 768–4140. Fax (214) 768–2701     

The 1982-83 Eruption at Galunggung Volcano, Java (Indonesia): Oxygen Isotope Geochemistry of a Chemically Zoned Magma Chamber

Mount Galunggung is a historically active volcano in southwesternJava that has erupted four times in the last two centuries.During the most recent event, which occurred during a 9–monthinterval in 1982– 83, some 305 10⁶ m³ of medium–K,calc–alkaline magma was erupted. This eruption was unusualbecause of its duration, the diversity of eruption dynamicsand products, and the range of lava compositions produced. Thecomposition of juvenile material changed gradually during thecourse of the eruption from initial plagioclase (An_60–75)and two–pyrozene bearing andesites with 58% SiO₂ to finalplagioclase (An_85–90), diopside, and olivine (Fo_85–90)bearing primitive magnesium basalts with 47% SiO₂ Mineralogicaland compositional relationships indicate a magmatic evolutioninvolving differentitation of high–Mg parental melt. Theeruptive volumes of 35 10⁶ m³ andesite, 120 10⁶ m³ maficandesite, and 150 10⁶ m³ basalt are consistent with the ideathat the 1982– 83 eruption progressively tapped and draineda magma chamber that had become chemically stratified throughextensive crystal fractionation. Separates of plagioclase and pyroxene have ¹⁸O( SMO W) rangesof + 5. 6 to + 6.0 and + 5.3 to + 5.6, respectively, with ¹⁸O_plag–pxvalues of + 0.4 to + 0.6o, indicating internal O–isotopeequiliburium at temperature of 1100–850 C. The magenesianbasalts have magmatic ¹⁸O/ ¹⁶O ratios similar to those of mid–oceanridge basalt, and the O–isotope ratios of compositionallyevolved derivative melts show no evidence for contaminationof the galunggung magmas by ¹⁸O–rich crust during differentiation.Andesites and transitional mafic and sites have a more variableO–isotope character, with laves and phenocrysts havingboth higher and lower ¹⁸O values than observed in the parentalmagnesium basalts. These features are interpreted to reflectintramagma chamber processes affecting the upper portions ofthe differentiating Galunggung magma body before the 1982–83eruption.     

Intersecting Isograds in the Whetstone Lake Area, Ontario

Pelitic and calcareous rocks in the Whetstone Lake area havean unusually wide range of chemical composition. Metamorphicreactions have been deduced that represent the observed ‘discontinuities’in compatible mineral assemblages, and by plotting the reactantand the product assemblage of each reaction on a map, metamorphicisograds have been delincated ‘from both sides’.For the pelitic rocks, successively higher-grade isograds arebased on the following reactions: (1)chlorite+muscovite+garnetstaurolite+biotite+quartz+water; (2) chlorite+muscovite+staurolite+quartz kyanite+biotite+water; (3) kyanitesillimanite; (4)staurolite+museovite+quartzsillimanite+garnet+biotite+water. A fifth isograd, based on the reaction (5) biotite+calcite+quartzCa-amphibole+K-feldspar+carbon dioxide+water intersects the isograds based on reactions (2), (3), and (4)in such a manner as to indicate that the H₂O/CO₂ fugacity ratiowas significantly higher in the vicinity of a granite plutonthan in the metasedimentary rocks remote from the pluton. Chemicalanalyses of the coexisting minerals in reaction (5) indicatethat the real reaction may involve plagioclase, epidote, sphene,and Fe-Ti oxides as well.     

Thermodynamic Mixing Properties of Muscovite-Paragonite Crystalline Solutions at High Temperatures and Pressures, and their Geological Applications

Reversed Na-K exchange data between mica and a 2 molal aqueous(Na,K)Cl fluid (Flux & Chatterjee, 1986) have been employedto model the thermodynamic mixing behaviour of muscovite-paragonitecrystalline solutions on the basis of the Redlich-Kister equation.For these binary micas, G^ex_m may be expressed as where A=11222+1.389 T+0.2359 P, B=–1134+6.806 T–0.0840 P, and C=–7305+9.043 T, with T in K, P in b, G^ex_m, A, B, and C in joules/mol. G_m^ex is well constrained between 450 and 620?C, and may be extrapolatedbeyond that range with caution. The calculated solvi are skewedtoward the paragonite end member. In the range up to 15 kb,the critical temperature, T_c and the critical composition, X_cmay be expressed as a function of P by the relations: and with P indicated in bars. Calculated phase relations of muscovite-paragonite crystallinesolutions have been depicted in terms of the system KAlSi₃O₈-NaAlSi₃O₈-Al₂O₃-SiO₂-H₂O.These data may be applied to appropriate assemblages involvingmica, alkali feldspar, an Al₂ polymorph, and quartz to estimateP, T and a_H2O conditions of their equilibration. In principle,the muscovite limb of the solvus may be used to obtain geothermometricdata for coexisting muscovite-paragonite pairs, provided theequilibrium pressure is independently known. However, such applicationmust be restricted for the present to micas on the ideal muscovite-paragonitejoin. Mica-alkali feldspar-Al₂SiO₅-quartz or mica-plagioclase-Al₂SiO₅-quartzassemblages may be used to deduce a_H2O in the coexisting fluid,if P, and T of equilibrium are independently known. Examplesof such geological applications are given.     

Melting of a Hydrous Mantle: II. Geochemistry of Crystals and Liquids Formed by Anatexis of Mantle Peridotite at High Pressures and High Temperatures as a Function of Controlled Activities of Water, Hydrogen, and Carbon Dioxide

The system peridotite-H₂O–CO₂ serves as a simplified modelfor the phase relations of mantle peridotite involving morethan one volatile component. Run products obtained in a studyof phase relations of four mantle peridotites in the presenceof H₂O- and (H₂O+CO₂)- bearing vapors and with controlled hydrogenfugacity (f_H2) at high pressures and temperatures have beensubjected to a detailed chemical investigation, principallyby the electron microprobe. Mg/(Mg+Fe) of all phases generally increases with increasingtemperature and with increasing Mg/(Mg+Fe) of the starting material.This ratio appears to decrease with increasing pressure forolivine, and for amphibole coexisting with garnet. Decreasingf_H2 from that of IW buffer to that of MH buffer decreases Mg/(Mg+Fe)of the partial melt from approximately 0-85 to approximately0.50, whereas the Fo content of coexisting olivine increasesslightly less than 3 per cent and the Mg/(Mg+Fe) of clinopyroxeneincreases about 4 per cent. However, the variations in Fo contentof olivines are within those observed in olivines from naturalmantle peridotite. The chemistry of other silicate mineralsdoes not significantly reflect variations of f_H2. Consequently,the peridotite mineralogy and/or chemistry is not a good indicatorfor the f_H2 conditions during crystallization. All crystalline phases, except amphibole, and to some extentgarnet, show increasing Cr content with increasing temperatureand increasing Cr content of the starting material, resultingin a positive correlation with Mg/(Mg+Fe). Partial melts aredepleted in Cr₂O₃ relative to the crystalline phases. High Mg/Mg+Fe)and Cr₂O₃ are thus expected in crystal residues after partialmelting. The absolute values depend on degree of melting andthe composition of the parent peridotite. Liquids formed by anatexis of mantle peridotite are andesiticunder conditions of X_H2O^v > 0.6 to at least 25 kb total pressureand to more than 200?C above the peridotite solidus. This observationsupports numerous suggestions that andesite genesis in islandarcs may result from partial melting of underlying peridotitemantle. In contrast to basaltic rocks, the absence of amphibole(paragasitic hornblende) does not affect the silica-saturatednature of the liquids. Increasing K₂O content of the startingmaterial (up to 1 wt. per cent K₂O) results in increasing potassiumcontent of the amphibole (1 wt. per cent K₂O) as well as theappearance of phlogopite. The liquid under these conditionsis relatively K₂0-poor (less than 1 wt. per cent K₂O). Partial melts are olivine normative with X_H2O 0.5, and initialliquids contain normative ol and ne at X_H2O 0.4. The alkalinityof these liquids increases with decreasing X_H2O below valuesof 0.5. The (ol+opx)-normative liquids resemble oceanic basaltswhereas (ol+ne)-normative liquids resemble olivine nepheliniteand melilite basalt. Low aHlo and high a_Co2 conditions may bethose under which kimberlites and related rocks are formed inthe mantle.     

Alteration of a Komatiite Flow from Alexo, Ontario, Canada

To investigate the ability of komatiites to preserve duringalteration a record of the geochemical and isotopic compositionof the Archean mantle, we studied the petrology and geochemistryof a komatiite flow from Alexo, Ontario. Although this flowis relatively well preserved, two main types of alteration arerecognized: (1) hydration of variable intensity throughout thewhole flow; (2) local rodingitization. In samples only slightlyaffected by hydration, the alteration was essentially isochemical;where more intense, hydration was accompanied by the mobilityof TiO₂, Zr and the light rare-earth elements (LREE). The mobilityof these reputedly immobile trace elements is influenced bytexture and secondary mineral assemblages. Rodingitization wasaccompanied by still greater mobility. An Nd isochron with anage of 272698 Ma and Nd_(T) =+ 2.5 is defined by wholerock samples.Because the spread of Sm-Nd ratios is far greater than can beexplained by magmatic processes, the age is interpreted as thatof the main alteration event during or soon after emplacement.Scattered initial Sr isotopic ratios and Nd _(T) (+ 3.6 to +0.7)provide evidence for several younger events. The Nd (T) of magnaticclinopyroxene ( plus;3.8) is higher than that of mafic tofelsicrocks and pyroxenes from the Abibiti belt (Nd _(T) +2.5). Thisresult implies: (1) the komatiites exchanged Nd with surroundingrocks during waterrock interaction; (2) the isotopic compositionof komatiites and their mantle source differed from that ofthe more common basalts of the Abitibi belt. KEY WORDS: alteration; Archean; Komatiite; trace elements; radiogenic and stable islotopes ^*Present address: Ore Genesis Research Group, VIEPS Department of Earth Science, Monash University, Clayton, Vic 3168, Australia. Telephone: (61) 3 9905-3881. Fax: (61) 3 9905–4903. e-mail: ylahaye{at}artemis.earth.monash.edu.au     

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination     

Magmatic Differentiation at an Island-arc Caldera: Okmok Volcano, Aleutian Islands, Alaska

Okmok volcano is situated on oceanic crust in the central Aleutianarc and experienced large (15 km³) caldera-forming eruptionsat 12 000 years BP and 2050 years BP. Each caldera-forming eruptionbegan with a small Plinian rhyodacite event followed by theemplacement of a dominantly andesitic ash-flow unit, whereaseffusive inter- and post-caldera lavas have been more basaltic.Phenocryst assemblages are composed of olivine + pyroxene +plagioclase ± Fe–Ti oxides and indicate crystallizationat 1000–1100°C at 0·1–0·2 GPain the presence of 0–4% H₂O. The erupted products followa tholeiitic evolutionary trend and calculated liquid compositionsrange from 52 to 68 wt % SiO₂ with 0·8–3·3wt % K₂O. Major and trace element models suggest that the moreevolved magmas were produced by 50–60% in situ fractionalcrystallization around the margins of the shallow magma chamber.Oxygen and strontium isotope data (¹⁸O 4·4–4·9,⁸⁷Sr/ ⁸⁶Sr 0·7032–0·7034) indicate interactionwith a hydrothermally altered crustal component, which led toelevated thorium isotope ratios in some caldera-forming magmas.This compromises the use of uranium–thorium disequilibria[(²³⁰Th/ ²³⁸U) = 0·849–0·964] to constrainthe time scales of magma differentiation but instead suggeststhat the age of the hydrothermal system is 100 ka. Modellingof the diffusion of strontium in plagioclase indicates thatmany evolved crystal rims formed less than 200 years prior toeruption. This addition of rim material probably reflects theremobilization of crystals from the chamber margins followingreplenishment. Basaltic recharge led to the expansion of themagma chamber, which was responsible for the most recent caldera-formingevent. KEY WORDS: Okmok; caldera; U-series isotopes; Sr-diffusion; time scales; Aleutian arc     

Age and Geochemistry of Basement and Alkalic Rocks of Malaita and Santa Isabel, Solomon Islands, Southern Margin of Ontong Java Plateau

Geochemical and ⁴⁰ Ar—³⁹ Ar studies of the Malaita OlderSeries and Sigana Basalts, which form the basement of Malaitaand the northern portion of Santa Isabel, confirm the existenceof Ontong Java Plateau (OJP) crust on these islands. Sr, Nd,and Pb isotopic ratios of Malaita Older Series and Sigana lavasfall within limited ranges [(⁸⁷Sr/⁸⁶Sr)T= 0.70369–0.70423,E_Nd(T)= + 3.7 to +6.0, and ²⁰⁶Pb/²⁰⁴Pb = 18.25–18.64]virtually indistinguishable from those found in the three OJPbasement drill sites as far as 1600 km away, indicating a uniformhotspot-like mantle source with a slight ‘Dupal’signature for the world's largest oceanic plateau. Three chemicaltypes of basalts are recognized, two of which are equivalentto two of the three types drilled on the plateau, and one withno counterpart, as yet, on the plateau; the chemical data indicateslightly different, but all high, degrees of melting and slightvariation in source composition. All but one of the ⁴⁰Ar-³⁹Arplateau ages determined for Malaita Older Series and SiganaBasalt lavas are identical to those found at the distant drillsites: 121.30.9 Ma and 92.01.6 Ma, suggesting that two short-lived,volumetrically important plateau-building episodes took place30 m.y. apart. Aside from OJP lavas, three isotopically distinctsuites of alkalic rocks are present. The Sigana Alkalic Suitein Santa Isabel has an ⁴⁰ Ar-³⁹ Ar age of 91.70.4 Ma, the sameas that of the younger OJP tholeiites, yet it displays a distinct’HIMU‘ -type isotopic signature [²⁰⁶Pb/²⁰⁴Pb 20.20,(⁸⁷Sr/⁸⁶Sr) T 0.7032, _Nd(T) 4.4], possibly representing small-degreemelts of a minor, less refractory component in the OJP mantlesource region. The Younger Series in southern Malaita has an⁴⁰Ar-³⁹Ar age of 44 Ma and isotopic ratios [_Nd(T)=-0.5 to +1.0,(⁸⁷Sr/⁸⁶Sr)_T =0.70404–0.70433, ²⁰⁶Pb/²⁰⁴Pb = 18.57–18.92]partly overlapping those of the ‘PHEM’ end-memberpostulated for Samoa, and those of present-day Rarotonga lavas;one or both of these hotspots may have caused alkalic volcanismon the plateau when it passed over them at 44 Ma. The NorthMalaita Alkalic Suite in northernmost Malaita is probably ofsimilar age, but has isotopic ratios [(⁸⁷Sr/⁸⁶Sr) _T 0.7037,_Nd(T) +4.5, ²⁰⁶pb/²⁰⁴pb 18.8) resembling those of some OJP basementlavas; it may result from a small amount of melting of agedplateau lithosphere during the OJP's passage over these hotspots.Juxtaposed against OJP crust in Santa Isabel is an 62–46-Maophiolitic (sensu lato) assemblage. Isotopic and chemical datareveal Pacific-MORB-like, backarc-basin-like, and arc-like signaturesfor these rocks, and suggest that most formed in an arc—backarcsetting before the Late Tertiary collision of the OJP againstthe old North Solomon Trench. The situation in Santa Isabelappears to provide a modern-day analog for some Precambriangreenstone belts. KEY WORDS: oceanic plateaux; Ontong Java Plateau; Solomon Islands; Sr-Nd-Pb isotopes; age and petrogenesis ^*Corresponding author.     

Phase Equilibria of Amphibolites from the Post Pond Volcanics, Mt. Cube Quadrangle, Vermont

Amphibolites of the Post Pond Volcanics, south-west corner ofthe Mt. Cube Quadrangle, Vermont, are characterized by a greatdiversity of bulk rock types that give rise to a wide varietyof low-variance mineral assemblges. Original rock types arebelieved to have been intrusive and extrusive volcanics, hydrothermallyaltered volcanics and volcanogenic sediments with or withoutadmixtures of sedimentary detritus. Metamorphism was of staurolite-kyanitegrade. Geothermometry yields a temperature of 535 ± 20°C at pressures of 5–6 kb. Partitioning of Fe and Mg between coexisting phases is systematic,indicating a close approach to chemical equilibrium was attained.Relative enrichment of Fe/Mg is garnet > staurolite >gedrite > anthophyllite cummingtonite hornblende > biotite> chlorite > wonesite > cordierite dolomite > talc;relative enrichment in Mn/Mg is garnet > dolomite > gedrite> staurolite cummingtonite > hornblende > anthophyllite> cordierite > biotite > wonesite > chlorite >talc. between coexisting amphiboles varies as a function ofbulk Fe/Mg, which is inconsistent with an ideal molecular solutionmodel for amphiboles. Mineral assemblages are conveniently divided into carbonate+ hornblende-bearing, hornblende-bearing (carbonate-absent)and hornblende-absent. The carbonate-bearing assemblages allcontain hornblende + dolomite+ calcite + plagioclase (andesineand/or anorthite) + quartz with the additional phases garnetand epidote (in Fe-rich rocks) and chlorite ± cummingtonite(in magnesian rocks). Carbonate-bearing assemblages are restrictedto the most calcic bulk compositions. Hornblende-bearing (carbonate absent) assemblages occur in rocksof lower CaO content than the carbonate-bearing assemblages.All of these assemblages contain hornblende + andesine ±quartz + Fe-Ti oxide (rutile in magnesian rocks and ilmenitein Fe-rich rocks). In rocks of low Al content, cummingtoniteand two orthoamphiboles (gedrite and anthophyllite) are common.In addition, garnet is found in Fe-rich rocks and chlorite isfound in Mg-rich rocks. Several samples were found that containhornblende + cummingtonite + gedrite + anthophyllite ±garnet +chlorite + andesine + quartz + Fe-Ti oxide ±biotite. Aluminous assemblages contain hornblende + staurolite+ garnet ± anorthite/bytownite (coexisting with andesine)± gedrite ± biotite ± chlorite ±andesine ± quartz ± ilmenite. Hornblende-absentassemblages are restricted to Mg-rich, Ca-poor bulk compositions.These rocks contain chlorite ± cordierite ± staurolite± talc ± gedrite ± anthophyllite ±cummingtonite ± garnet ± biotite ± rutile± quartz ± andesine. The actual assemblage observeddepends strongly on Fe/Mg, Ca/Na and Al/Al + Fe + Mg. The chemistry of these rocks can be represented, to a firstapproximation, by the model system SiO₂–Al₂O₃–MgO–FeO–CaO–Na₂O–H₂O–CO₂;graphical representation is thus achieved by projection fromquartz, andesine, H₂O and CO₂ into the tetrahedron Fe–Ca–Mg–Al.The volumes defined by compositions of coexisting phases filla large portion of this tetrahedron. In general, the distributionof these phase volumes is quite regular, although in detailthere are a large number of phase volumes that overlap otherphase volumes, especially with respect to Fe/Mg ratios. Algebraicand graphical analysis of numerous different assemblages indicatethat every one of the phase volumes should shift to more magnesiancompositions with decreasing µ_H2O. It is therefore suggestedthat the overlapping phase volumes are the result of differentassemblages having crystallized in equilibrium with differentvalues of µ_H2O or µ_CO2 and that the different valuesmay have been inherited from the original H₂O and CO₂ contentof the volcanic prototype. If true, this implies that eithera fluid phase was not present during metamorphism, or that fluidflow between rocks was very restricted.     

Basalt and Sediment Geochemistry and Magma Petrogenesis in a Transect from Oceanic Island Arc to Rifted Continental Margin Arc: the Kermadec--Hikurangi Margin, SW Pacific

Sediment mixing and recycling through a subduction zone canbe detected in lead isotopes and trace elements from basaltsand sediments from the Kermadec-Hikurangi Margin volcanic arcsystem and their coupled back-arc basins. Sr, Nd and Pb isotopesfrom the basalts delineate relatively simple, almost overlapping,arrays between back-arc basin basalts of the Havre Trough-NgatoroBasin (⁸⁷Sr/⁸⁶Sr = 0.70255; _Nd=+9.3; ²⁰⁶Pb/²⁰⁴Pb = 18.52; ²⁰⁸Pb/²⁰⁴Pb= 38.18), island arc basalts from the Kermadec Arc togetherwith basalts from Taupo Volcanic Zone (⁸⁷Sr/⁸⁶Sr 0.7042; _Nd= +5; ²⁰⁶Pb/²⁰⁴Pb= 18.81; ²⁰⁸Pb/²⁰⁴Pb = 38.61), and sedimentsderived from New Zealand's Mesozoic (Torlesse) basement (⁸⁷Sr/⁸⁶Sr 0.715; _Nd —4; ²⁰⁶Pb/²⁰⁴Pb 18.86; ²⁰⁸Pb/²⁰⁴Pb 38.8).Basalts from the arc front volcanoes have high Cs, Rb, Ba, Th,U and K, and generally high but variable Ba/La, Ba/Nb ratios,characteristic of subduction-related magmas, relative to typicaloceanic basalts. These signatures are diluted in the back-arcbasins, which are more like mid-ocean ridge basalts. Strongchemical correlations in plots of SiO₂ vs CaO and loss on ignitionfor the sediments (finegrained muds) are consistent with mixingbetween detrital and biogenic (carbonate-rich) components. Otherdata, such as Zr vs CaO, are consistent with the detrital componentcomprising a mixture of arc- and continent-derived fractions.In chondrite-normalized diagrams, most of the sediments havelight rare earth element enriched patterns, and all have negativeEu anomalies. The multielement diagrams have negative spikesat Nb, P and Ti and distinctive enrichments in the large ionlithophile elements and Pb relative to mantle. Isotopic measurementsof Pb, Sr and Nd reveal restricted fields of Pb isotopes butwide variation in Nd and Sr relative to other sediments fromthe Pacific Basin. Rare K-rich basalts from Clark Volcano towardthe southern end of the oceanic Kermadec Island Arc show unusualand primitive characteristics ( 2% K₂O at 50% SiO₂, Ba 600p.p.m., 9–10% MgO and Ni > 100 p.p.m.) but have highlyradiogenic Sr, Nd and Pb isotopes, similar to those of basaltsfrom the continental Taupo Volcanic Zone. These oceanic islandarc basalts cannot have inherited their isotope signatures throughcrustal contamination or assimilation—fractional crystallizationtype processes, and this leads us to conclude that source processesvia bulk sediment mixing, fluid and/or melt transfer or somecombination of these are responsible. Although our results showclear chemical gradients from oceanic island arc to continentalmargin arc settings (Kermadec Arc to Taupo Volcanic Zone), overlapbetween the data from the oceanic and continental sectors suggeststhat the lithospheric (crustal contamination) effect may beminimal relative to that of sediment subduction. Indeed, itis possible to account for the chemical changes by a decreasenorthward in the sediment flux into the zone of magma genesis.This model receives support from recent sediment dispersal studiesin the Southern Ocean which indicate that a strong bottom current(Deep Western Boundary Current) flows northward along the easterncontinental margin of New Zealand and sweeps continental derivedsediment into the sediment-starved oceanic trench system. Thetrace element and isotopic signatures of the continental derivedcomponent of this sediment are readily distinguished, but alsodiluted in a south to north direction along the plate boundary. KEY WORDS: subduction zone basalts; sediments; Sr-, Nd-, Pb-isotopes; trace elements ^*Present address: School of Earth Sciences, University of Melbourne, Parkville, Vic. 3052, Australia.     

Melting of a Hydrous Mantle: I. Phase Relations of Natural Peridotite at High Pressures and Temperatures with Controlled Activities of Water, Carbon Dioxide, and Hydrogen

Four natural peridotite nodules ranging from chemically depletedto Fe-rich, alkaline and calcic (SiO₂=43?7–45?7 wt. percent, Al₂O3=1?6O–8?21 wt. per cent, CaO=0?70–8?12wt. per cent,alk=0?10–0?90 wt. per cent and Mg/(Mg+Fe²⁺)=0?94–0?85)have been investigated in the hypersolidus region from 800?to 1250?C with variable activities of H₂O, CO₂, and H₂. Thevapor-saturated peridotite solidi are 50–200?C below thosepreviously published. The temperature of the beginning of meltingof peridotite decreases markedly with decreasing Mg/(Mg+Fe)of the starting material at constant CaO/Al₂O₃. Conversely,lowering CaO/Al₂O₃ reduces the temperature at constant Mg/(Mg+Fe)of the starting material. Temperature differences between thesolidi up to 200?C are observed. All solidi display a temperatureminimum reflecting the appearance of garnet. This minimum shiftsto lower pressure with decreasing Mg/(Mg+Fe) of the startingmaterial. The temperature of the beginning of melting decreasesisobarically as approximately a linear function of the mol fractionof H₂O in the vapor (X_H2O). The data also show that some CO₂may dissolve in silicate melts formed by partial melting ofperidotite. Amphibole (pargasitic hornblende) is a hypersolidus mineralin all compositions, although its P/T stability field dependson bulk rock chemistry. The upper pressure stability of amphiboleis marked by the appearance of garnet. The vapor-saturated (H₂O) liquidus curve for one peridotiteis between 1250? and 1300?C between 10 and 30 kb. Olivine, spinel,and orthopyroxene are either liquidus phases or coexist immediatelybelow the temperature of the peridotite liquidus. The data suggest considerable mineralogical heterogeneity inthe oceanic upper mantle because the oceanic geotherm passesthrough the P/T band covering the appearance of garnet in variousperidotites. The variable depth to the low-velocity zone is explained byvariable a_H2O conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. It is suggested that komatiite in Precambrian terrane couldform by direct melting of hydrous peridotite. Such melting requiresabout 1250?C compared with 1600?C which is required for drymelting. The genesis of kimberlite can be related to partial meltingof peridotite under conditions of (). Such activities of H₂Oresult in melting at depths ranging between 125 and 175 km inthe mantle. This range is within the minimum depth generallyaccepted for the formation of kimberlite.     

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.