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.     

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     

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     

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     

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     

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     

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     

Origin and Evolution of Silicic Magmatism at Yellowstone Based on Ion Microprobe Analysis of Isotopically Zoned Zircons

The origin of large-volume Yellowstone ignimbrites and smaller-volumeintra-caldera lavas requires shallow remelting of enormous volumesof variably ¹⁸O-depleted volcanic and sub-volcanic rocks alteredby hydrothermal activity. Zircons provide probes of these processesas they preserve older ages and inherited ¹⁸O values. This studypresents a high-resolution, oxygen isotope examination of volcanismat Yellowstone using ion microprobe analysis with an averageprecision of ± 0·2 and a 10 µm spot size.We report 357 analyses of cores and rims of zircons, and isotopeprofiles of 142 single zircons in 11 units that represent majorYellowstone ignimbrites, and post-caldera lavas. Many zirconsfrom these samples were previously dated in the same spots bysensitive high-resolution ion microprobe (SHRIMP), and all zirconswere analyzed for oxygen isotope ratios in bulk as a functionof grain size by laser fluorination. We additionally reportoxygen isotope analyses of quartz crystals in three units. Theresults of this work provide the following new observations.(1) Most zircons from post-caldera low-¹⁸O lavas are zoned,with higher ¹⁸O values and highly variable U–Pb ages inthe cores that suggest inheritance from pre-caldera rocks exposedon the surface. (2) Many of the higher-¹⁸O zircon cores in theselavas have U–Pb zircon crystallization ages that postdatecaldera formation, but pre-date the eruption age by 10–20kyr, and represent inheritance of unexposed post-caldera sub-volcanicunits that have ¹⁸O similar to the Lava Creek Tuff. (3) Youngand voluminous 0·25–0·1 Ma intra-calderalavas, which represent the latest volcanic activity at Yellowstone,contain zircons with both high-¹⁸O and low-¹⁸O cores surroundedby an intermediate-¹⁸O rim. This implies inheritance of a varietyof rocks from high-¹⁸O pre-caldera and low-¹⁸O post-calderaunits, followed by residence in a common intermediate-¹⁸O meltprior to eruption. (4) Major ignimbrites of Huckleberry Ridge,and to a lesser extent the Lava Creek and Mesa Falls Tuffs,contain zoned zircons with lower-¹⁸O zircon cores, suggestingthat melting and zircon inheritance from the low-¹⁸O hydrothermallyaltered carapace was an important process during formation ofthese large magma bodies prior to caldera collapse. (5) The¹⁸O zoning in the majority of zircon core–rim interfacesis step-like rather than smoothly inflected, suggesting thatprocesses of solution–reprecipitation were more importantthan intra-crystalline oxygen diffusion. Concave-downward zirconcrystal size distributions support dissolution of the smallercrystals and growth of rims on larger crystals. This study suggeststhat silicic magmatism at Yellowstone proceeded via rapid, shallow-levelremelting of earlier erupted and hydrothermally altered Yellowstonesource rocks and that pulses of basaltic magma provided theheat for melting. Each post-caldera Yellowstone lava representsan independent homogenized magma batch that was generated rapidlyby remelting of source rocks of various ages and ¹⁸O values.The commonly held model of a single, large-volume, super-solidus,mushy-state magma chamber that is periodically reactivated andproduces rhyolitic offspring is not supported by our data. Rather,the source rocks for the Yellowstone volcanism were cooled belowthe solidus, hydrothermally altered by heated meteoric watersthat caused low ¹⁸O values, and then remelted in distinct pocketsby intrusion of basic magmas. Each packet of new melt inheritedzircons that retained older age and ¹⁸O values. This interpretationmay have significance for interpreting seismic data for crustallow-velocity zones in which magma mush and solidified areasexperiencing hydrothermal circulation occur side by side. Newbasalt intrusions into this solidifying batholith are requiredto form the youngest volcanic rocks that erupted as independentrhyolitic magmas. We also suggest that the Lava Creek Tuff magmawas already an uneruptable mush by the time of the first post-calderaeruption after 0·1 Myr of the climactic caldera-formingeruption. KEY WORDS: Yellowstone; oxygen isotopes; geochronology; isotope zoning; zircon; U–Pb dating; caldera; rhyolite; ion microprobe     

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     

Syros Metasomatic Tourmaline: Evidence for Very High-{delta}11B Fluids in Subduction Zones

High-pressure (HP) metamorphic blocks enclosed in a mafic toultramafic matrix from a mélange on the island of Syrosare rimmed by tourmaline-bearing reaction zones (blackwalls).The B isotopic composition of dravitic tourmaline within theseblackwalls was investigated in situ by secondary ion mass spectrometry.Boron in these tourmalines is unusually heavy, with ¹¹B valuesexceeding +18 in all investigated samples and reaching an extremevalue of +28·4 in one sample. Blackwalls formed duringexhumation of the HP mélange at a depth of 20–25km at temperatures of 400–430°C, by influx of externalhydrous fluids. The compositions of the fluids are estimatedto be in the range of 100–300 µg/g B with ¹¹B valuesof +18 to +28. The high ¹¹B values cannot be explained by tourmalineformation from unmodified slab-derived fluids. However, suchfluids could interact with the material in the exhumation channelon their way from the dehydrating slab to the site of tourmalineformation in the blackwalls. This could produce exceptionallyhigh ¹¹B values in the fluids, a case that is modelled in thisstudy. The model demonstrates that subduction fluids may beeffectively modified in both trace element and isotopic compositionduring their migration through the material overlying the subductingslab. Blackwall tourmaline from Syros has a large grain size(several centimetres), high abundance, and an exceptionallyhigh ¹¹B value. The formation of tourmaline at the contact betweenmafic or felsic HP blocks and their ultramafic matrix involvedfluids released during dehydration reactions in the subductingslab. It forms a heavy-boron reservoir in hybrid rocks overlyingthe subducting slab, and may, thus, have a significant impacton the geochemical cycle of B and its isotopes in subductionzones. KEY WORDS: boron isotopes; tourmaline; subduction zone; fluid, high pressure     

Oxygen Isotope Geochemistry of the Lassen Volcanic Center, California: Resolving Crustal and Mantle Contributions to Continental Arc Magmatism

This study reports oxygen isotope ratios determined by laserfluorination of mineral separates (mainly plagioclase) frombasaltic andesitic to rhyolitic composition volcanic rocks eruptedfrom the Lassen Volcanic Center (LVC), northern California.Plagioclase separates from nearly all rocks have ¹⁸O values(6·1–8·4) higher than expected for productionof the magmas by partial melting of little evolved basalticlavas erupted in the arc front and back-arc regions of the southernmostCascades during the late Cenozoic. Most LVC magmas must thereforecontain high ¹⁸O crustal material. In this regard, the ¹⁸O valuesof the volcanic rocks show strong spatial patterns, particularlyfor young rhyodacitic rocks that best represent unmodified partialmelts of the continental crust. Rhyodacitic magmas erupted fromvents located within 3·5 km of the inferred center ofthe LVC have consistently lower ¹⁸O values (average 6·3± 0·1) at given SiO₂ contents relative to rockserupted from distal vents (>7·0 km; average 7·1± 0.1). Further, magmas erupted from vents situated attransitional distances have intermediate values and span a largerrange (average 6·8 ± 0·2). Basaltic andesiticto andesitic composition rocks show similar spatial variations,although as a group the ¹⁸O values of these rocks are more variableand extend to higher values than the rhyodacitic rocks. Thesefeatures are interpreted to reflect assimilation of heterogeneouslower continental crust by mafic magmas, followed by mixingor mingling with silicic magmas formed by partial melting ofinitially high ¹⁸O continental crust (9·0) increasinglyhybridized by lower ¹⁸O (6·0) mantle-derived basalticmagmas toward the center of the system. Mixing calculationsusing estimated endmember source ¹⁸O values imply that LVC magmascontain on a molar oxygen basis approximately 42 to 4% isotopicallyheavy continental crust, with proportions declining in a broadlyregular fashion toward the center of the LVC. Conversely, the¹⁸O values of the rhyodacitic rocks suggest that the continentalcrust in the melt generation zones beneath the LVC has beensubstantially modified by intrusion of mantle-derived basalticmagmas, with the degree of hybridization ranging on a molaroxygen basis from approximately 60% at distances up to 12 kmfrom the center of the system to 97% directly beneath the focusregion. These results demonstrate on a relatively small scalethe strong influence that intrusion of mantle-derived maficmagmas can have on modifying the composition of pre-existingcontinental crust in regions of melt production. Given thisresult, similar, but larger-scale, regional trends in magmacompositions may reflect an analogous but more extensive processwherein the continental crust becomes progressively hybridizedbeneath frontal arc localities as a result of protracted intrusionof subduction-related basaltic magmas. KEY WORDS: oxygen isotopes; phenocrysts; continental arc magmatism; Cascades; Lassen     

A Stable Isotope Study of Anorogenic Magmatism in East Central Asia

A stable isotope study of 168 plutonic igneous rock and fivewater samples from Transbaikalia, East Asia, has been made,including 318 whole-rock and mineral ¹⁸O/¹⁶O analyses and 14D/H analyses. This represents the first detailed isotopic studyof the enormous Phanerozoic K-rich (mostly anorogenic) granitoidbelts of this region, which are thousands of kilometers in lengthand span an age range of >250Ma. Of the five main intrusivesuites, emplacement of the youngest (Permo-Triassic) was accompaniedby intense meteoric-hydrothermal activity, locally causing extreme¹⁸O depletio (¹⁸O _feldspar<–12). This reflects thevery low ¹⁸O of the water involved in these systems, which probablyhad ¹⁸O < – 20 and D < – 150, consistent withthe high paleolatitude of Transbaikalia in the early Mesozoic(80N). Despite local post-emplacement, hydrothermal ¹⁸O-depletioneffects near Permo-Triassic and younger plutons, the variationof magmatic isotopic composition in the five intrusive suites,in space and time, can be clearly discerned using the ¹⁸O/¹⁶Ovariation in phases such as quartz and sphene that are resistantto sub-solidus exchange. A procedure for analyzing ¹⁸O/¹⁶O insphene using a laser fluorination technique is described: analysisof samples as small as 0.4 mg (including single crystals ofsphene from granitoids) is possible and provides an effectiveway to estimate the magmatic ¹⁸O value of plutonic igneous rocks.Most sphene and quartz ¹⁸O values vary by 1.0–2.0% withineach of the five main intrusive suites in Transbaikalia (rangingin age from mid-Paleozoic to Mesozoic), and are uniform bothwithin individual plutons and among plutons of the same suiteseparated by tens or hundreds of kilometers. However, each suitehas a unique range in ¹⁸O/¹⁶O, indicating that, on a regionalscale, the magmatic ¹⁸O values of these granitoids decreasedprogressively in 1% decrements from +10 in the earliest groupto +6 in the youngest. This progression was accompanied by increasesin the concentration of elements such as K and Zr, and decreasesin the concentration of elements such as Sr and Ba. These systematicsrequire large scale deep crustal melting and mixing processesto generate the compositional uniformity of individual plutonsand groups over such wide areas, and also a progressive hybridizationof the crust with alkalic, mantle-derived magmas to generatesyenites and granites with progressively lower ¹⁸O values. Thisprocess may be a hallmark of anorogenic granitoid petrogenesisand the intracontinental cratonization process in general, andalso represents an important (though largely cryptic) crustalgrowth mechanism. KEY WORDS: anorogenic granitoids; crustal growth; hybridization; hydrothermal systems; stable isotopes ¹Present address: Galson Sciences Limited, 5 Grosvenor House, Melton Road, Oakham LE15 6AX, UK.     

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     

Oxygen and Hydrogen Isotope Stratigraphy of the Rustenburg Layered Suite, Bushveld Complex: Constraints on Crustal Contamination

New ¹⁸O values for plagioclase, pyroxene and olivine, and limitedwhole-rock D values are presented for samples from the RustenburgLayered Suite of the Bushveld Complex, South Africa. In combinationwith existing data, these provide a much more complete compositeO-isotope stratigraphy for the intrusion. Throughout the layeredsuite, mineral ¹⁸O values indicate that the magmas from whichthey crystallized had ¹⁸O values that were about 7·1,that is, 1·4 higher than expected for mantle-derivedmagmas, suggesting extensive crustal contamination. More limitedH-isotope data suggest that the OH present within whole rocks,regardless of the degree of alteration, is of magmatic originand not an alteration phenomenon. There appears to be no systematicchange in ¹⁸O value with stratigraphic height and this requiresthe contamination to have taken place in a ‘staging chamber’before emplacement of the magma(s) into the present chamber.Large amounts (30–40%) of contamination by the lower tomiddle crust are needed to explain these ¹⁸O values, which isin general agreement with previous estimates based on Sr- andNd-isotope data. Alternatively, smaller amounts of contamination(20%) by sedimentary rocks, or their partial melts, representedby the country rock can explain the data, but it is not apparenthow such material could have been present at the depth of the‘staging chamber’ in the lower to middle crust. KEY WORDS: Bushveld Complex; Rustenburg Layered Suite; oxygen isotopes; hydrogen isotopes; crustal contamination     

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     

Thermal Anomalies In A Regional Metamorphic Terrane: An Isotopic Study of the Role of Fluids

A series of ten localized, high-temperature, granulite faciesregions occurs within the regional metamorphic, sillimanitezone of New Hampshire, USA. These regions, or ‘hot spots’,measure 10–30km² in a sillimanite zone that extends 50kmeast-west and over 150km north-south. The hot spots are characterizedby an abrupt increase in temperature over a distance of a fewkilometers, from 550?C in the sillimanite zone to 700?C in thegranulite facies. Mineral assemblages in pelites change rapidlyover the same distance from sillimanite-staurolite-muscovite-garnet-biotite-quartzto sillimanite-K feldspar-cordierite-garnet-biotite-quartz inthe granulite facies. The hot spot located near Bristol, New Hampshire was chosenfor detailed study because it has a network of quartz-graphiteveins in its core. Oxygen isotope analyses of minerals and rocksfrom Bristol suggest a close approach to pervasive exchangeequilibration between disparate rock types throughout the sillimanitezone. A comparison between chlorite zone pelites and calc-silicategranofelses of equivalent stratigraphic age shows a range ofover 7 in ¹⁸O of whole rocks from lower grade, whereas sillimanitezone rocks from Bristol vary by no more than 3, only. Quartzseparated from the Bristol high-grade metasediments varies byno more than 2?3. Superimposed upon the regional, sillimanite-zone oxygen isotopehomogenization is a 1–2 km wide region in the core ofthe hot spot in which the ¹⁸O of metasediments has been furtherhomogenized. Both quartz from quartz-graphite veins and quartzfrom cordierite-bearing wall rocks have exchanged oxygen isotopes;all quartz has ¹⁸O=13?8?0?5 (SMOW). Radiometric ages of quartz-graphite veins and metasedimentarywall rocks show that the hydrothermal event and metamorphismin the hot spot were both of Acadian age. Hydrothermal overgrow-thson zircons from one of the veins give ages of 409 ? 6 Ma. Monazitefrom cordierite bearing pelites from the wall of the same veingives a U-Pb age of 392 ? 3 Ma, using conventional techniques. The coincidence of: (1) an isograd high; (2) an isotherm hotspot; (3) a network of quartz-graphite veins; and (4) an oxygenisotope alteration halo suggests a relationship between hydrothermalactivity and heating of metasediments. The geochronologicalevidence demonstrates that the hydrothermal event and hot spotmetamorphism were not greatly separated in time. It is proposedthat the hot spots represent loci where hot metamorphic fluidswere focused through a fracture system now recorded by quartz-graphiteveins.     

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