Staurolite Stability in a Part of the System Fe-Al-Si-O-H

The following reactions, believed to be analogous to those whichdefine the maximum extent of staurolite-quartz compatibilityat moderate oxygen fugacity in metamorphic rocks, have beendetermined in terms of hydrous fluid pressure and temperature.The O: H composition ratio of the fluid was controlled withthe quartz-fayalite-magnetite (QFM) buffer assemblage. (I) Fe-staurolitequartz almandine+sillimanite+water. (II) Fe-staurolitequartz Fe-cordierite+sillimanite+water. (III) Fe-chloritoid+sillimanite Fe-staurolite+quartz+water. In addition, two reactions which delineate part of the stabilitylimits of Fe-cordierite have been investigated: (IV) Fe-cordierite almandine+sillimanite+quartz. (V) Fe-cordierite hercynite+sillimanite+quartz. The experimental information has been used to predict boundariesto the PT fields of all quartz and QFM-buffered fluid-bearingassemblages involving Fe-staurolite, Fe-cordierite, Fe-chloritoid,almandine, and sillimanite. Using information from this andother studies, three mineral assemblages are recognized whichare stable at similar temperatures but different fluid pressures.In order of decreasing pressure they are: (a) Above 5 kb: staurolite, quartz, kyanite, fluid; (b) Between 1.5 and 8.5 kb (outer limits; in natural rocks thisfield will have a much narrower pressure range) staurolite,quartz, cordierite, fluid. (c) Below 3.5 kb: Fe-cordierite, andalusite, fluid of oxygenfugacity equivalent to the quartz-fayalite-magnetite assemblage. These phase assemblages may be the equivalents of naturallyoccurring mineral facies, but this must be proven in the field.In addition the absence of cordierite from rocks of appropriatecomposition and temperature of formation betokens total pressuresgreater than 3–5 kb. ¹Present address: Grant Institute of Geology, West Mains Road, Edinburgh 9, Scotland.     

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.     

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     

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.     

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     

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     

An Experimental Determination of Iron Biotite-Alkali Feldspar Equilibria

Experiments in the system KAlSi0₄-NaAlSi0₄-SiOj-Fe-0-H indicatethat approximately 20 mole per cent of sodium annite [NaFe₃AlSiO₁₀(OH)₂]can enter into solid solution with potassium annite. This substitutionreduces the biotite stability field. With excess alkali feldsparand no free quartz, the following reactions limit the biotitestability: Feldspar(s)+biotite feldspar(s)+magnetite+vapor. (1) Feldspar+biotite feldspar+fayalite+leucite+vapor. (2) Feldspar+biotite feldspar+fayalite+liquid+vapor. (3) Biotite feldspar+fayalite+nepheline+vapor. (4) On the QFM buffer (P_Total = 2 Kb), reaction 1 occurs at 685°C in the sodium free system and at 625 °C when twofeldspars are present; on NNO, it occurs at 630 and 590 °C.On the G-CH buffer, reaction 2 is stable at high temperatures(795–830 °Q and potassic compositions (), reaction3 at intermediate conditions (T = 740–95 °C; ) andreaction 4 at lower temperatures (710–40 °C) and sodiccompositions (). In the presence of excess quartz, reaction1 remains stable below the QFM buffer, but the reaction Feldspars)+biotite+quartz feldspars)+fayalite+vapor (5) is stable at higher hydrogenfugacities. On the G-CH buffer, reaction 5 occurs at 610 °Cin the sodium free system and at 595 °C when two alkalifeldspars are present. On the MW buffer, the temperatures are585 and 515 °C (M.I.). The experimental data presented suggest that biotite will notbe stable in the presence of granitic liquids at total pressuresbelow 4 kb, providing the fluorine and titanium content of thebiotite is low. They also suggest that gradients in the a£1S,l0 in a rock could produce variations in the biotite Fe/Fe+Mgratio and in extreme cases could result in the complete breakdown(decreased ) of biotite or its crystallization (increased )where previously there was none.     

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     

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 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     

Chloritoid, and the Isochemical Character of Barrow's Zones

It is argued that despite poverty of outcrop the apparent restrictionof chloritoid to a wedge-shaped area at the north-eastern extremityof Barrow's zones is real. Two possible interpretations of thisrestriction are considered: (a) That the chloritoid producingreaction (as yet unidentified) was characterized by a lowerP/T than that of the reaction muscovite+ chlorite+chloritoid+quartz staurolite+biotite+H²O, whereby, with increasing grade, chloritoidgives way to staurolite. A pressure gradient increasing fromnorth-east to south-west (postulated on separate grounds, Chinner,1966) would then result in the convergence of the chloritoidand staurolite isograds towards the south-west, and the eventualsuppression of the chloritoid isograd to give the wedge-shapedoutcrop actually found, (b) The lack of low-grade hydrous assemblagesaluminous enough to give chloritoid or staurolite with increasinggrade suggests that the low-grade limit of chloritoid (and,to the south-west, of staurolite) may not be an isograd, buta chemical boundary. Such a boundary could either be metasedimentary,or metasomatic, representing an alkali gradient of the typestudied by Orville, in which, essentially, potassium and waterreleased within the high-grade metamorphic zones have migratedto low-grade zones to form more micaceous assemblages. The widespreadexistence of ‘shimmer aggregate‘ muscovite alterationof aluminous minerals in thesillimanite, kyanite, and staurolitezones provides evidence of potassium transfer during the waneof metamorphic temperatures on a scale comparable to that which,during the main metamorphic imprint, would have been requiredto mask the development of peraluminous assemblages in the chlorite,biotite, and garnet zones.     

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.     

Zircon Hf Isotopic Evidence for Mixing of Crustal and Silicic Mantle-derived Magmas in a Zoned Granite Pluton, Eastern Australia

Zircon Hf isotopic data from a zoned pluton of the Moonbi supersuite,New England batholith, eastern Australia, are consistent withmagma mixing between two silicic melts, each derived from isotopicallydistinct sources. Although zircons from three zones within theWalcha Road pluton give a U–Pb crystallization age of249 ± 3 Ma, zircon populations from each zone have arange in _Hf. Zircons from the mafic hornblende–biotitemonzogranite pluton margin and intermediate zones have _Hf +5to +11, whereas those from the more felsic centre of the plutonhave _Hf +7 to +16, representing a total variation of 11 _Hfunits. The Lu–Hf depleted mantle model ages range from650 to 250 Ma, with the younger zircons present only in thefelsic pluton centre. The variation in _Hf indicates the involvementof silicic melts from at least two sources, one a crustal componentwith a Neoproterozoic model age and the other a primitive mantle-derivedcomponent with model ages similar to the U–Pb crystallizationage of the pluton. The zircons reflect the isotopic compositionsof the different proportions of crustal-derived silicic melt,relative to mantle-derived silicic melt, between melt generationand final pluton construction. The Walcha Road pluton is consideredto have formed by incremental assembly of progressively morefelsic melt batches resulting from mixing, replenishment andcrystal–melt separation, with final pluton constructioninvolving mechanical concentration as zones of crystal mush.The zoned pluton and, more broadly, the Moonbi supersuite provideexamples of magma mixing by which the more silicic units havemore juvenile isotopic compositions as a result of increasingproportions of residual melt from basalt fractionation, relativeto crustal partial melt. KEY WORDS: Australia; granite magma mixing; zircon; zoned pluton; Hf isotopes     

The Gronnedal-Ika Carbonatite-Syenite Complex, South Greenland: Carbonatite Formation by Liquid Immiscibility

The Grønnedal-Ika complex is dominated by layered nephelinesyenites which were intruded by a xenolithic syenite and a centralplug of calcite to calcite–siderite carbonatite. Aegirine–augite,alkali feldspar and nepheline are the major mineral phases inthe syenites, along with rare calcite. Temperatures of 680–910°Cand silica activities of 0·28–0·43 weredetermined for the crystallization of the syenites on the basisof mineral equilibria. Oxygen fugacities, estimated using titanomagnetitecompositions, were between 2 and 5 log units above the fayalite–magnetite–quartzbuffer during the magmatic stage. Chondrite-normalized REE patternsof magmatic calcite in both carbonatites and syenites are characterizedby REE enrichment (La_CN–Yb_CN = 10–70). Calcite fromthe carbonatites has higher Ba (5490 ppm) and lower HREE concentrationsthan calcite from the syenites (54–106 ppm Ba). This isconsistent with the behavior of these elements during separationof immiscible silicate–carbonate liquid pairs. _Nd(T =1·30 Ga) values of clinopyroxenes from the syenites varybetween +1·8 and +2·8, and _Nd(T) values of whole-rockcarbonatites range from +2·4 to +2·8. Calcitefrom the carbonatites has ¹⁸O values of 7·8 to 8·6and ¹³C values of –3·9 to –4·6. ¹⁸Ovalues of clinopyroxene separates from the nepheline syenitesrange between 4·2 and 4·9. The average oxygenisotopic composition of the nepheline syenitic melt was calculatedbased on known rock–water and mineral–water isotopefractionation to be 5·7 ± 0·4. Nd and C–Oisotope compositions are typical for mantle-derived rocks anddo not indicate significant crustal assimilation for eithersyenite or carbonatite magmas. The difference in ¹⁸O betweencalculated syenitic melts and carbonatites, and the overlapin _Nd values between carbonatites and syenites, are consistentwith derivation of the carbonatites from the syenites via liquidimmiscibility. KEY WORDS: alkaline magmatism; carbonatite; Gardar Province; liquid immiscibility; nepheline syenite     

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     

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     

Experimental Petrology of a Highly Potassic Magma

The melting behaviour of a highly potassic biotite mafuriteof the Central African olivine leucitite kindred has been studiedexperimentally as a function of pressure (to 30kb) temperature,and water content (0%, 5%, 15%, 25%, and 40% H₂O). Olivine isthe liquidus phase up to 30 kb for all water contents studiedexcept for anhydrous (clinopyroxene on the liquidus) and 15%H₂O (phlogopite on the liquidus) conditions. Analyses of phasescrystallizing from the biotite mafurite show that pressure hasvery little effect on the composition of clinopyroxene whichis extremely calcium-rich, and low in Al₂O₃ and TiO₂ for allconditions investigated. Phlogopite has low TiO₂ content andtitanphlogopite cannot be a refractory phase in the upper mantlecausing Ti-depletion in partial melts in equilibrium with titanphlogopite.There are apparently no conditions where the extremely potassicbiotite mafurite could be a partial melt from pyrolite but derivationfrom an olivine+clinopyroxene+phlogopite+ilmenite assemblageoccurring as ‘enriched’ patches in the upper mantle,is possible. Liquids in equilibrium with phlogopite as a residualphase at 30 kb would be olivine nephelinites with approximately5% K₂O, Na₂O/K₂O 1 and TiO₂ > 5+. Crystal elutriation withtransported residual phlogopite reacting (phlogopite+liquid1 olivine+liquid 2) at lower pressures provides a mechanismfor K-enrichment and generating Na₂O/K₂O < 1.     

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     

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     

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.