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 model forthe phase relations of mantle peridotite involving more thanone volatile component. Run products obtained in a study ofphase relations of four mantle peridotites in the presence ofH₂O- 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. DecreasingfH₂from 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 fH₂. Consequently,the peridotite mineralogy and/or chemistry is not a good indicatorfor the fH₂ 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.     

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.     

Properties of Synthetic Triclinic KFeSi3O8, Iron-microcline, with some Observations on the Iron-microcline{rightleftharpoons}Iron-sanidine Transition

Triclinic KFeSi₃O₈, iron-microcline, has been synthesized fromoxide mixes and by complete conversion of monoclinic KFeSi₃O₈,iron-sanidine. Iron-microcline is triclinic, C, a=8?68?0?01?, b=13?10?0?01, c=7?34?0?01, =90? 45'?10', ß=116?03'?10', =86?14'?10'. The optical properties (Na light) are:=1?585?0?002, ß=1?596?0?002, =1?605?0?002, 2V=85?(calc.), Xb, Z c=20??5?. A reversible phase transition betweentriclinic and monoclinic KFeSi₃O₈ occurs at 704??6? C at 2000bars total pressure. Iron-microcline is the low-temperaturepolymorph; no intermediate polymorphs were observed in eitherhydrothermal or dry heating experiments.     

A Method for Thermodynamical Calculation of Basicity Indicators of Rocks and Minerals

A new method has been suggested for evaluating the overall basicityof minerals and rocks by using ionization reactions involvingone proton: (sum of cations) + H₂O = mineral + H⁺, (sum of cations) + H₂O = (sum of normative minerals of a rock)+ H⁺. The basicity indicators are expressed as standard free energychanges of these reactions (). At standard water pressure (logP_H2O = 0) and chemical activity of the metal ions ( log _Mⁿ⁺= 0), the relationship between and alkalinity of solutions(pH) becomes: = –2.303 RTlog _H⁺ = 2.303 RT pH. The overall basicities of rock-forming oxides, minerals andmajor rocks were calculated from the thermodynamic data on ionsin water solutions and solid compounds.     

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.     

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     

Open-System Magma Chamber Evolution: an Energy-constrained Geochemical Model Incorporating the Effects of Concurrent Eruption, Recharge, Variable Assimilation and Fractional Crystallization (EC-E'RA{chi}FC)

Significant petrogenetic processes governing the geochemicalevolution of magma bodies include magma Recharge (includingformation of ‘quenched inclusions’ or enclaves),heating and concomitant partial melting of country rock withpossible ‘contamination’ of the evolving magma body(Assimilation), and formation and separation of cumulates byFractional Crystallization (RAFC). Although the importance ofmodeling such open-system magma chambers subject to energy conservationhas been demonstrated, the effects of concurrent removal ofmagma by eruption and/or variable assimilation (involving imperfectextraction of anatectic melt from wall rock) have not been considered.In this study, we extend the EC-RAFC model to include the effectsof Eruption and variable amounts of assimilation, A. This model,called EC-E'RAFC, tracks the compositions (trace elements andisotopes), temperatures, and masses of magma body liquid (melt),eruptive magma, cumulates and enclaves within a composite magmaticsystem undergoing simultaneous eruption, recharge, assimilationand fractional crystallization. The model is formulated as aset of 4 + t + i + s coupled nonlinear differential equations,where the number of trace elements, radiogenic and stable isotoperatios modeled are t, i and s, respectively. Solution of theEC-E'RAFC equations provides values for the average temperatureof wall rock (T_a), mass of melt within the magma body (M_m),masses of cumulates (M_ct), enclaves (M_en) and wall rock () and the masses of anatectic melt generated () and assimilated (). In addition, t trace element concentrations and i + s isotopic ratios inmelt and eruptive magma (C_m, _m, _m), cumulates (C_ct, _m, _m), enclaves(C_en, , ) and anatectic melt (C_a, , ) as a function of magma temperature (T_m) are also computed. Input parametersinclude the (user-defined) equilibration temperature (T_eq),a factor describing the efficiency of addition of anatecticmelt () from country rock to host magma, the initial temperatureand composition of pristine host melt (, , , ), recharge melt (, , , ) and wall rock (, , , ), distribution coefficients (D_m, D_r, D_a) and their temperaturedependences (H_m, H_r, H_a), latent heats of transition (meltingor crystallization) for wall rock (h_a), pristine magma (h_m)and recharge magma (h_r) as well as the isobaric specific heatcapacity of assimilant (C_p,a), pristine (C_p,m) and recharge(C_p,r) melts. The magma recharge mass and eruptive magma massfunctions, M_r(T_m) and M_e(T_m), respectively, are specified apriori. M_r(T_m) and M_e(T_m) are modeled as either continuous orepisodic (step-like) processes. Melt productivity functions,which prescribe the relationship between melt mass fractionand temperature, are defined for end-member bulk compositionscharacterizing the local geologic site. EC-E'RAFC has potentialfor addressing fundamental questions in igneous petrology suchas: What are intrusive to extrusive ratios (I/E) for particularmagmatic systems, and how does this factor relate to rates ofcrustal growth? How does I/E vary temporally at single, long-livedmagmatic centers? What system characteristics are most profoundlyinfluenced by eruption? What is the quantitative relationshipbetween recharge and assimilation? In cases where the extractionefficiency can be shown to be less than unity, what geologiccriteria are important and can these criteria be linked to fieldobservations? A critical aspect of the energy-constrained approachis that it requires integration of field, geochronological,petrologic, and geochemical data, and, thus, the EC-ERAFC ‘systems’approach provides a means for answering broad questions whileunifying observations from a number of disciplines relevantto the study of igneous rocks. KEY WORDS: assimilation; energy conservation; eruption; open system; recharge     

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     

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     

Hafnium Isotope and Trace Element Constraints on the Nature of Mantle Heterogeneity beneath the Central Southwest Indian Ridge (13{degrees}E to 47{degrees}E)

Hafnium isotope and incompatible trace element data are presentedfor a suite of mid-ocean ridge basalts (MORB) from 13 to 47°Eon the Southwest Indian Ridge (SWIR), one of the slowest spreadingand most isotopically heterogeneous mid-ocean ridges. Variationsin Nd–Hf isotope compositions and Lu/Hf ratios clearlydistinguish an Atlantic–Pacific-type MORB source, presentwest of 26°E, characterized by relatively low _Hf valuesfor a given _Nd relative to the regression line through all Nd–Hfisotope data for oceanic basalts (termed the ‘Nd–Hfmantle array line’; the deviation from this line is termed_Hf) and low Lu/Hf ratios, from an Indian Ocean-type MORB signature,present east of 32°E, characterized by relatively high _Hfvalues and Lu/Hf ratios. Additionally, two localized, isotopicallyanomalous areas, at 13–15°E and 39–41°E,are characterized by distinctly low negative and high positive_Hf values, respectively. The low _Hf MORB from 13 to 15°Eappear to reflect contamination by HIMU-type mantle from thenearby Bouvet mantle plume, whereas the trace element and isotopiccompositions of MORB from 39 to 41°E are most consistentwith contamination by metasomatized Archean continental lithosphericmantle. Relatively small source-melt fractionation of Lu/Hfrelative to Sm/Nd, compared with MORB from faster-spreadingridges, argues against a significant role for garnet pyroxenitein the generation of most central SWIR MORB. Correlations between_Hf and Sr and Pb isotopic and trace element ratios clearly delineatea high-_Hf ‘Indian Ocean mantle component’ that canexplain the isotope composition of most Indian Ocean MORB asmixtures between this component and a heterogeneous Atlantic–Pacific-typeMORB source. The Hf, Nd and Sr isotope compositions of IndianOcean MORB appear to be most consistent with the hypothesisthat this component represents fragments of subduction-modifiedlithospheric mantle beneath Proterozoic orogenic belts thatfoundered into the nascent Indian Ocean upper mantle duringthe Mesozoic breakup of Gondwana. KEY WORDS: mid-ocean ridge basalt; isotopes; incompatible elements; Indian Ocean     

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.     

Stable Isotopic Evidence for Fluid-Rock Interactions in the Ivrea Zone, Italy

Stable isotope compositions of Ivrea Zone marbles and associatedlithologies are in general heterogeneous. The oxygen isotopecomposition of quartz in pelites ranges from ¹⁸O +9 to + 17(SMOW) and does not vary systematically with metamorphic grade.Peridotites retain oxygen isotope signatures close to mantlevalues. Marble calcites vary in isotopic composition from ¹³C + 2(PDB),¹⁸0 +24(SMOW)to ¹³C –6(PDB), ¹⁸O + 13 (SMOW).Depletions in ¹⁸O and ¹³C may be explained dominantly by interactionwith fluids derived from within the observed metasedimentarysequence during prograde metamorphism. ¹⁸O and ¹³C show gradients of greater than 5/m across marblemargins and within marbles. The preservation of such isotopicgradients is not consistent with the long-term presence of grain-boundary-scaleinterconnected fluid films in and around marbles. There is ageneral lowering of ¹⁸O within individual marble bodies althoughlarge carbon and oxygen isotopic gradients are present. Calcitein marbles may attain oxygen isotope equilibrium, but rarelycarbon isotope equilibrium, with surrounding metapelites. Infiltrationof marbles must involve a component of channelized fluid flow. The general lack of isotopic equilibration within the sequencerequires channelized fluid flow and limited fluid-rock ratios.Large pervasive mantle to crust fluid fluxes are not consistentwith the observations. ^*Present address: Natural Environment Research Council, Polaris House, North Star Avenue, Swindon SN2 1EU, England     

Petrogenesis of the Swaziland and Northern Natal Rhyolites of the Lebombo Rifted Volcanic Margin, South East Africa

The Jozini and Mbuluzi rhyolites and Oribi Beds of the southernLebombo Monocline, southeastern Africa, have geochemical characteristicsthat indicate they were derived by partial melting of a mixtureof high-Ti/Zr and low-Ti/Zr Sabie River Basalt Formation types.Compositional variations within the different rhyolite typescan largely be explained by subsequent fractional crystallization.The Sr- and Nd-isotope composition of the rhyolites is uniqueamongst Gondwana silicic large igneous provinces, having _Ndvalues close to Bulk Earth (–0·94 to 0·35)and low, but more variable, initial ⁸⁷Sr/⁸⁶Sr ratios (0·7034–0·7080).Quartz phenocryst ¹⁸O values indicate that the rhyolite magmashad ¹⁸O values between 5·3 and 6·7, consistentwith derivation from a basaltic protolith with ¹⁸O values between4·8 and 6·2. The low-¹⁸O rhyolites (< 6·0)come from the same stratigraphic horizon and are overlain andunderlain by rhyolites with more ‘normal’ ¹⁸O magmavalues. These low-¹⁸O rhyolites cannot have been produced byfractional crystallization or partial melting of mantle-derivedbasaltic material. The rhyolites have low water contents, makingit unlikely that the low ¹⁸O values are the result of post-emplacementalteration. Modification of the source by fluid–rock interactionat elevated temperatures is the most plausible mechanism forlowering the ¹⁸O magma value. It is proposed that the low-¹⁸Orhyolites were derived by melting of earlier altered rhyolitein calderas situated to the east, which were not preserved afterGondwana break-up. KEY WORDS: rhyolite; Lebombo; stable and radiogenic isotopes; low-¹⁸O magmas; partial melting     

Petrographic, Chemical and B-Isotopic Insights into the Origin of Tourmaline-Rich Rocks and Boron Recycling in the Martinamor Antiform (Central Iberian Zone, Salamanca, Spain)

Tourmaline in the Martinamor antiform occurs in tourmalinites(rocks with >15–20% tourmaline by volume), clasticmetasedimentary rocks of the Upper Proterozoic Monterrubio formation,quartz veins, pre-Variscan orthogneisses and Variscan graniticrocks. Petrographic observations, back-scattered electron (BSE)images, and microprobe data document a multistaged developmentof tourmaline. Overall, variations in the Mg/(Mg + Fe) ratiosdecrease from tourmalinites (0·36–0·75),through veins (0·38–0·66) to granitic rocks(0·23–0·46), whereas Al increases in thesame order from 5·84–6·65 to 6·22–6·88apfu. The incorporation of Al into tourmaline is consistentwith combinations of ^xAl(NaR)_–1 and AlO(R(OH))_–1exchange vectors, where ^x represents X-site vacancy and R is(Mg + Fe²⁺ + Mn). Variations in ^x/(^x + Na) ratios are similarin all the types of tourmaline occurrences, from 0·10to 0·53, with low Ca-contents (mostly <0·10apfu). Based on field and textural criteria, two groups of tourmaline-richrocks are distinguished: (1) pre-Variscan tourmalinites (probablyCadomian), affected by both deformation and regional metamorphismduring the Variscan orogeny; (2) tourmalinites related to thesynkinematic granitic complex of Martinamor. Textural and geochemicaldata are consistent with a psammopelitic parentage for the protolithof the tourmalinites. Boron isotope analyses of tourmaline havea total range of ¹¹B values from –15·6 to 6·8;the lowest corresponding to granitic tourmalines (–15·6to –11·7) and the highest to veins (1·9to 6·8). Tourmalines from tourmalinites have intermediate¹¹B values of –8·0 to +2·0. The observedvariations in ¹¹B support an important crustal recycling ofboron in the Martinamor area, in which pre-Variscan tourmaliniteswere remobilized by a combination of mechanical and chemicalprocesses during Variscan deformation, metamorphism and anatexis,leading to the formation of multiple tourmaline-bearing veinsand a new stage of boron metasomatism. KEY WORDS: tourmalinites; metamorphic and granitic rocks; mineral chemistry; whole-rock chemistry; boron isotopes     

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.per cent, A1₂O₃ = 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 hypersolidusregion from 800? to 1250?C with variable activities of H₂O,CO₂, and H₂. The vapor-saturated peridotite solidi are 50–200?Cbelow those previously published. The temperature of the beginningof melting of peridotite decreases markedly with decreasingMg/(Mg+SFe) of the starting material at constant CaO/Al₂O₃.Conversely, lowering CaO/Al₂O₃ reduces the temperature at constantMg/(Mg+Fe) of the starting material. Temperature differencesbetween the solidi up to 200?C are observed. All solidi displaya temperature minimum reflecting the appearance of garnet. Thisminimum shifts to lower pressure with decreasing Mg/(Mg + Fe)of the starting material. The temperature of the beginning ofmelting decreases isobarically as approximately a linear functionof the mol fraction of H₂O in the vapor (X_H2O^v). The data alsoshow that some CO₂ may dissolve in silicate melts formed bypartial melting of peridotite. 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 co-exist 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 aHjo conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. Itis suggested that komatiite in Precambrian terrane could formby 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 X_H2O^v = 0.5–0.25 (X_CO2^v= 0.5–0.75). Such activities of H₂O result in meltingat depths ranging between 125 and 175 km in the mantle. Thisrange is within the minimum depth generally accepted for theformation of kimberlite.     

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     

Sources and Petrogenesis of Late Triassic Dolerite Dikes in the Liaodong Peninsula: Implications for Post-collisional Lithosphere Thinning of the Eastern North China Craton

A combination of major and trace element, whole-rock Sr, Ndand Hf isotope, and zircon U–Pb isotopic data are reportedfor a suite of dolerite dikes from the Liaodong Peninsula inthe northeastern North China Craton. The study aimed to investigatethe source, petrogenesis and tectonic setting of the dikes.Sensitive high-resolution ion microprobe U–Pb zircon analysesyield a Late Triassic emplacement age of 213 Ma for these dikes,post-dating the collision between the North China and Yangtzecratons and consequent ultrahigh-pressure metamorphism. Threegeochemical groups of dikes have been identified in the LiaodongPeninsula based on their geochemical and Sr–Nd–Hfisotope characteristics. Group 1 dikes are tholeiitic, withhigh TiO₂ and total Fe₂O₃ and low MgO contents, absent to weaknegative Nb and Ta anomalies, variable (⁸⁷Sr/⁸⁶Sr)_i (0·7060–0·7153),_Nd(t) (– 0·8 to –6·5) and _Hf(t) (–2·7to –7·8) values, and negative _Hf(t) (–1·1to –7·8). They are inferred to be derived frompartial melting of a relatively fertile asthenospheric mantlein the spinel stability field, with some upper crustal assimilationand fractional crystallization. Group 2 dikes have geochemicalfeatures of high-Mg andesites with (⁸⁷Sr/⁸⁶Sr)_i values of 0·7063–0·7072,and negative _Nd(t) (–3·0 to –9·5)and _Hf(t) (–3·2 to –10·1) values,and may have originated as melts of foundered lower crust, withsubsequent interaction with mantle peridotite. Group 3 dikesare shoshonitic in composition with relatively low (⁸⁷Sr/⁸⁶Sr)_ivalues (0·7061–0·7063), and negative _Nd(t)(–13·2 to –13·4) and _Hf(t) (–11·0to –11·5) values, and were derived by partial meltingof an ancient, re-enriched, refractory lithospheric mantle inthe garnet stability field. The geochemical and geochronologicaldata presented here indicate that Late Triassic magmatism occurredin an extensional setting, most probably related to post-orogeniclithospheric delamination. KEY WORDS: mafic dike; asthenospheric mantle; lithospheric mantle; delamination; North China Craton     

Genesis of Ultramafic Lamprophyres and Carbonatites at Aillik Bay, Labrador: a Consequence of Incipient Lithospheric Thinning beneath the North Atlantic Craton

Numerous dykes of ultramafic lamprophyre (aillikite, mela-aillikite,damtjernite) and subordinate dolomite-bearing carbonatite withU–Pb perovskite emplacement ages of 590–555 Ma occurin the vicinity of Aillik Bay, coastal Labrador. The ultramaficlamprophyres principally consist of olivine and phlogopite phenocrystsin a carbonate- or clinopyroxene-dominated groundmass. Ti-richprimary garnet (kimzeyite and Ti-andradite) typically occursat the aillikite type locality and is considered diagnosticfor ultramafic lamprophyre–carbonatite suites. Titanianaluminous phlogopite and clinopyroxene, as well as comparativelyAl-enriched but Cr–Mg-poor spinel (Cr-number < 0.85),are compositionally distinct from analogous minerals in kimberlites,orangeites and olivine lamproites, indicating different magmageneses. The Aillik Bay ultramafic lamprophyres and carbonatiteshave variable but overlapping ⁸⁷Sr/⁸⁶Sr_i ratios (0·70369–0·70662)and show a narrow range in initial _Nd (+0·1 to +1·9)implying that they are related to a common type of parentalmagma with variable isotopic characteristics. Aillikite is closestto this primary magma composition in terms of MgO (15–20wt %) and Ni (200–574 ppm) content; the abundant groundmasscarbonate has ¹³C_PDB between –5·7 and –5,similar to primary mantle-derived carbonates, and ¹⁸O_SMOW from9·4 to 11·6. Extensive melting of a garnet peridotitesource region containing carbonate- and phlogopite-rich veinsat 4–7 GPa triggered by enhanced lithospheric extensioncan account for the volatile-bearing, potassic, incompatibleelement enriched and MgO-rich nature of the proto-aillikitemagma. It is argued that low-degree potassic silicate to carbonatiticmelts from upwelling asthenosphere infiltrated the cold baseof the stretched lithosphere and solidified as veins, therebycrystallizing calcite and phlogopite that were not in equilibriumwith peridotite. Continued Late Neoproterozoic lithosphericthinning, with progressive upwelling of the asthenosphere beneatha developing rift branch in this part of the North Atlanticcraton, caused further veining and successive remelting of veinsplus volatile-fluxed melting of the host fertile garnet peridotite,giving rise to long-lasting hybrid ultramafic lamprophyre magmaproduction in conjunction with the break-up of the Rodinia supercontinent.Proto-aillikite magma reached the surface only after coatingthe uppermost mantle conduits with glimmeritic material, whichcaused minor alkali loss. At intrusion level, carbonate separationfrom this aillikite magma resulted in fractionated dolomite-bearingcarbonatites (¹³C_PDB –3·7 to –2·7)and carbonate-poor mela-aillikite residues. Damtjernites maybe explained by liquid exsolution from alkali-rich proto-aillikitemagma batches that moved through previously reaction-lined conduitsat uppermost mantle depths. KEY WORDS: liquid immiscibility; mantle-derived magmas; metasomatism, Sr–Nd isotopes; U–Pb geochronology     

An Oxygen and Hydrogen Isotope Study of the Skaergaard Intrusion and its Country Rocks: a Description of a 55 M.Y. Old Fossil Hydrothermal System

Oxygen isotope analyses have been obtained on rocks and coexistingminerals, principally plagioclase and clinopyroxene, from about400 samples of the Skaergaard layered gabbro intrusion and itscountry rocks. The ¹⁸O values of plagioclase decrease upwardin the intrusion, from ‘normal’ values of about+6.0 to +6.4 in the Lower Zone and parts of the Middle Zone,to values as low as –2.4 in the Upper Border Group. The¹⁸O depletions of the plagioclase all took place under subsolidusconditions, and were produced by the Eocene meteoric-hydrothermalsystem established by this pluton. Clinopyroxene, which is moreresistant to ¹⁸O exchange than is plagioclase, also underwentdepletion in ¹⁸O, but to a lesser degree (¹⁸O = +5.2 to +3.5).The ¹⁸O-depleted rocks typically show reversed ¹⁸Oplag–pxfractionations, except at the top of the Upper Zone, where thepyroxenes are very fine-grained aggregates pseudomorphous afterferrowollastonite; these inverted pyroxenes were much more susceptibleto subsolidus ¹⁸O exchange (¹⁸O = +3–9 to +0.7). D/H analysesof the chloritized basalt country rocks and of the minor quantitiesof alteration minerals in the pluton (D = –116 to –149)confirm these interpretations, indicating that the rocks interactedwith meteoric groundwaters having an original D –100.and ¹⁸O –14. Low D values ( –125) were also foundthroughout the biotites of the Precambrian basement gneiss,requiring that small amounts of water penetrated downward todepths of at least 6 to 10 km. These values, together with thelack of ¹⁸O depletion of the gneiss, imply that the overallwater/rock ratios were very small in that unit (<0.01), andthus that convective circulation of these waters was much morevigorous in the overlying highly jointed plateau basalts (¹⁸O –4.0 to +4–0) than in the relatively impermeablegneiss (¹⁸O +7–3 to +7–7). This contrast in permeabilitiesof the country rocks is also reflected in the distribution of¹⁸O values in the pluton; the plagioclases with ‘normal’¹⁸O values all lie stratigraphically beneath the projectionof the basalt-gneiss unconformity through the pluton. Elsewhere,the ¹⁸O depletions are correlated with abundance of fracturesand faults, particularly in the NE portion of the intrusion,where the Layered Series is very shallow-dipping and permeablebasalts underlie the gabbro. The transgressive granophyres in the lower part of the intrusivehave ¹⁸O values identical to those of the basement gneiss, indicatingthey were probably formed by partial melting of stoped blocksof gneiss. In the upper part of the intrusion these granophyredikes have ¹⁸O values similar to the adjacent host gabbro; thissuggests that much of the hydrothermal alteration occurred aftertheir emplacement. However, because of the rarity of low-temperaturehydrous alteration minerals, it is also clear that most of theinflux of H₂O into the layered gabbro occurred at very hightemperatures (>400–500 °C). Prior to flowing intothe gabbro, these fluids had exchanged with similar mineralassemblages in the basaltic country rocks, explaining the lackof chemical alteration of the gabbro. Xenoliths of roof rockbasalt and of Upper Border Group leucogabbro were strongly depletedin ¹⁸O by the hydrothermal system prior to their falling tothe bottom of the magma chamber and being incorporated in thelayered series. This proves that the hydrothermal system wasestablished very early, at the time of emplacement of the Skaergaardintrusion. However, no measurable ¹⁸O depletion of the gabbromagma could be detected, indicating that very little H₂O penetrateddirectly into the liquid magma, in spite of the fact that ahydrothermal circulation system totally enveloped the magmachamber for at least 100, 000 years during its entire periodof crystallization. Only as crystallization proceeded was thehydrothermal system able to collapse inward and interact withthe solidified and fractured portions of the gabbro. Neverthelesssome H₂O was clearly added directly to the magma by dehydrationof the stoped blocks of altered roof rock. It is also plausiblethat small amounts of meteoric water diffused directly intothe magma, most logically in the vicinity of major fracturezones that penetrated close to, or were underneath, the late-stagesheet of differentiated ferrodiorite magma. It is suggestedthat such influx of meteoric waters was responsible for manyof the gabbro pegmatite bodies that are common in the MarginalBorder Group; also, such H₂O might have produced local increasesin Fe⁺³/Fe⁺² in the magma that in turn could explain some ofthe asymmetric crystallization effects in the magma chamber.Local lowering of the liquidus temperature would also occur,perhaps leading to topographic irregularities on the floor ofthe magma chamber (e.g. the trough bands?).     

Fluid Flow During Contact Metamorphism at Mary Kathleen, Queensland, Australia

Corella marbles in the Mary Kathleen Fold Belt were infiltratedby fluids during low-pressure (200-MPa) contact metamorphismassociated with the intrusion of the Burstall granite at 1730–1740Ma. Fluids emanating from the granite [whole-rock (WR) ¹⁸O=8.1–8.6%]produced Fe-rich massive and banded garnet—clinopyroxeneskarns [¹⁸O(WR)=9.1–11.9%]. Outside the skarn zones, marblemineralogies define an increase in temperature (500 to >575C) and XCO₂ (0.05 to >0.12) towards the granite, andmost marbles contain isobarically univariant or invariant assemblagesin the end-member CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂system. Marbles have calcite (Cc) ¹⁸O and ¹³C values of 12.3–24.6%and –1.0 to –3.9%, respectively. A lack of down-temperaturemineral reactions in the marbles suggests that pervasive fluidinfiltration did not continue after the thermal peak of contactmetamorphism. The timing of fluid flow probably correspondsto a period of high fluid production and high intrinsic permeabilitiesduring prograde contact metamorphism. The petrology and stableisotope geochemistry of the marbles suggest that these rockswere infiltrated by water-rich fluids. If fluid flow occurredup to the peak of contact metamorphism, the mineralogical andisotopic resetting is best explained by fluids flowing up-temperaturetoward the Burstall granite. However, if fluid flow ceased beforthe peak of regional metamorphism, the fluid flow directioncannot be unambiguously determined. At individual outcrops,marble ¹⁸O(Cc) values vary by several permil over a few squaremetres, suggesting that fluid fluxes varied by at least an orderof magnitude on the metre to tens-of-metre scale. Fluids werefocused across lithological layering; however, mesoscopic fracturesare not recognized. The focusing of fluids was possibly viamicrofractures, and the variation in the degree of resettingmay reflect variations in microcrack density and fracture permeability.The marble—skarn contacts represent a sharp discontinuityin both major element geochemistry and ¹⁸O values, suggestingthat, at least locally, little fluid flow occurred across thesecontacts.