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 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     

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.     

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     

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     

Origin of Paleoproterozoic Komatiites at Jeesiorova, Kittila Greenstone Complex, Finnish Lapland

Komatiites from the 2 Ga Jeesiörova area in Finnish Laplandhave subchondritic Al₂O₃/TiO₂ ratios like those in Al-depletedkomatiites from Barberton, South Africa. They are distinct inthat their Al abundances are higher than those of the Al-depletedrocks and similar to levels in Al-undepleted komatiites. Moderatelyincompatible elements such as Ti, Zr, Eu, and Gd are enriched.Neither majorite fractionation nor hydrous melting in a supra-subductionzone setting could have produced these komatiites. Their highconcentrations of moderately incompatible elements may haveresulted from contamination of their parental melt through interactionwith metasomatic assemblages in the lithospheric mantle or enrichmentof their mantle source in basaltic melt components. Re–Osisotope data for chromite from the Jeesiörova rocks yieldan average initial ¹⁸⁷Os/¹⁸⁸Os of 0·1131 ± 0·0006(2), _Os(I) = 0·1 ± 0·5. These data, coupledwith an initial _Nd of +4, indicate that melt parental to thekomatiites interacted minimally with ancient lithospheric mantle.If their mantle source was enriched in a basaltic component,the combined Os–Nd isotopic data limit the enrichmentprocess to within 200 Myr prior to the formation of the komatiites.Their Os–Nd isotopic composition is consistent with derivationfrom the contemporaneous convecting upper mantle. KEY WORDS: Finnish Lapland; Jeesiörova; komatiites; mantle geochemistry; petrogenesis; redox state; Re/Os isotopes; Ti enrichment     

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     

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     

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     

Geochemical Constraints on the Origin of the Late Archean Skjoldungen Alkaline Igneous Province, SE Greenland

The present work reports the first broad geochemical investigationof the recently discovered late Archean (2700 Ma) Skjoldungenalkaline igneous province (SAP) in southeast Greenland. Therocks studied range in composition from ultramafic to felsicand comprise pyroxenites, hornblendites, hornblende noritesand diorites, monzonites, syenites, and nephelinitic rocks andcarbonatites. Various lithologic units from the host Archeangneissic basement are also investigated. The magmatic rocksshow remarkably coherent major element, trace element, rareearth element (REE), and Sr and Nd isotope systematics, suggestinga petrogenetic relationship. The most important geochemicalfeatures are high normative proportions of nepheline, forsteriteand albite, low TiO₂ (<15 wt %) and moderate FeO (total)(<12 wt %) contents, enrichments in large ion lithophileelements (LILE) and light rare earth elements both absoluteand relative to high field strength elements (HFSE) that displaylarge negative anomalies, and generally low to moderate abundancesof compatible elements. Field relations and REE and compatibleelement systematics among Skjoldungen rocks suggest that maficand ultramafic hornblende-rich samples may represent cumulatelithologies of the regional parental magma. On the basis ofmineral data, this is deduced to have had mg-number of 064,shoshonitic affinities (K₂O15 wt %), been close to silica saturationand volatile rich. Major element, trace element and REE systematicsfurther suggest that felsic intrusions are related to the maficregional parental magma through extensive olivine, hyperstheneand hornblende fractionation. Lack of correlation between La/Yband other critical trace and REE ratios indicates that apatite,zircon and titaniferous minerals were not important cumulusphases at advanced stages of evolution. The measured Sm–Ndwhole-rock isochron age is 2716 23 Ma (2 error) [mean squareof weighted deviates (MSWD) = 14], whereas linear regressionof the Sr isotope data yields an age of 26047 Ma (2 error)(MSWD = 22•2). The age obtained by Nd isotopes is corroboratedby U–Pb zircon results (2698 7 Ma), suggesting thatthe Sm–Nd system remained closed since crystallization.By contrast, the 100 Ma younger age obtained by Sr isotopessuggests that the Rb–Sr system has been disturbed. Initial¹⁴³Nd/¹⁴⁴ Nd ratios span a narrow range corresponding to _Nd(27Ga) =+074 to –109, whereas initial _Sr values at 27Ga cover a comparatively larger interval from –10 to +20.Neither initial _Nd nor initial _Sr values conform to previouslysuggested mantle depletion curves and no meaningful correlationexists between Nd and Sr isotopes for the Skjoldungen magmaticrocks as a whole. Although compositionally heterogeneous, theanalyzed suite of samples from the host agmatitic basement isextremely homogeneous with respect to age, with T^CHUR crustalresidence times around 2700–2800 Ma confirming limitedavailable isotopic evidence. Large-scale assimilation of Archeancrust or recycling of sediments derived from the local basementinto the mantle source fails to explain adequately negativeNb anomalies and low ^Nd signatures characteristic of the Skjoldungenintrusions. Rather, the nearchondritic isotopic compositionof Nd in the Skjoldungen samples together with the decoupledLILE and HFSE enrichment and slightly positive _Sr values areconsidered to reflect characteristics of the mantle source ina subduction zone environment. The geodynamic site hosting theSkjoldungen province thus may be an early manifestation of modern-styleplate tectonics. KEY WORDS: Skjoldungen province; Greenland; Archean; alkaline igneous rocks; geochronology; geochemistry ^*Corresponding author. Present address: Ecole Normale Suprieure de Lyon, 46 AlLe d'Italie, 69364 Lyon Cedex 07, France     

Re--Os and Sm--Nd Isotope Geochemistry of the Stillwater Complex, Montana: Implications for the Petrogenesis of the J-M Reef

Re—Os and Sm—Nd isotopic data have been obtainedfor mafic and ultramafic cumulates from the 2700-Ma StillwaterComplex and associated fine-grained sills and dykes, so as tobetter constrain the geochemical characteristics of Stillwaterparental magmas and to trace the source(s) of the precious metalsthat have been concentrated in the J-M Reef, the major platinum-groupelement mineral deposit in the complex. Initial Os isotopiccompositions (¹⁸⁷Os/¹⁸⁸Os) for chromitites from the Ultramaficseries range from a radiogenic isotopic composition of 0.1321(_Os = +21) for the platinum group element (PGE)-enriched B chromititeseam from the West Fork area to a near-chondritic isotopic compositionof 0.1069–0.1135 (_Os=–2 to +4.1) for the PGE-poorG and H chromitite seams, respectively, near the middle of theUltramafic series. Osmium isotopic data for the PGE-rich B chromititeseam are generally isochronous with whole-rock and mineral datafor the J-M Reef (_Os = + 12 to + 34). Re—Os isotopic datatherefore document a contrast between PGE-poor cumulates fromthe Ultramafic series and PGE-enriched cumulates from both theUltramafic series and the J-M Reef, suggesting that Os and probablythe other PGE were derived from at least two isotopically distinctsources. Moreover, these Re-Os isotopic characteristics correlatewith petrogenetic subdivisions of the Stillwater Complex basedon field mapping, petrology, REE geochemistry, and Sm—Ndisotope geochemistry. The data are best explained by mixingof two magma types, referred to as U-type and A-type magmas,with differing major element, trace element, and precious metalabundances and isotopic compositions. Although crustally contaminatedkomatiites can mimic the Os and Nd isotopic characteristicsof the U-type magma, the combination of low initial Os isotopicvalues (_Os0) with low initial Nd isotopic values (_Nd–1),high ²⁰⁷Pb/²⁰⁴Pb for a given ²⁰⁶Pb/²⁰⁴Pb (Wooden et al., 1991),and high (Ce/Yb)_n ratios in U-type cumulates and fine-grainedsills and dykes is more consistent with the involvement of aRe-poor, but trace-element-enriched portion of the subcontinentallithospheric mantle in the petrogenesis of Stillwater U-typemagmas. However, the radiogenic initial Os isotopic compositionsof the J-M Reef and other portions of the intrusion with elevatedPGE concentrations suggest that A-type parental magmas incorporatedOs from radiogenic early Archaean crust. The relatively largerange in (Ce/Yb)_n, _Os, and _Nd values suggests that mixing ofgeochemically distinct magmas may have been an important processthroughout the history of the Stillwater magma chamber. Magmamixing may then explain not only the PGE-enriched J-M Reef butalso the anomalous enrichment of the PGE in the B chromititeseam from the West Fork area and the variable values observedin other chromitite seams of the Ultramafic series. The intimateassociation of these magma types, derived from or modified inthe Archaean continental lithosphere, may then be crucial tothe formation of magmatic PGE mineral deposits.     

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     

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 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     

Age and Petrogenesis of Two Late Archean Magmatic Suites, Northwestern Superior Province, Canada: Zircon U-Pb and Lu-Hf Isotopic Relations

The paper presents U–Pb ages for zircon, titanite, andmonazite, and Hf isotopic data for zircon, from the rocks oftwo magmatic suites occurring mostly in the Archean Uchi Subprovinceand partly in the neighbouring Berens River and English Riversubprovinces of the northwestern Superior Province, Ontario.These data, together with observations on the morphologies and,where evident, the inheritance of the zircon crystals, constrainthe nature of the sources of the magmas and provide a recordof various crustal processes in their evolution. The older of the two magmatic suites formed at 2744–2740Ma along segments of a common arc system. The suite consistsof (1) several trondhjemitic to granodioritic plutons, with_Hf values of 6•1, intruded into older crust and possiblyformed from magma produced by partial melting of subducted,juvenile oceanic crust; (2) an assemblage of dacitic pyroclasticvolcanic rocks, with _Hf values of 3•2–4•0, associatedwith tholeiitic basalts and probably derived from magma meltedfrom arc mantle; and (3) a bimodal assemblage of tholeiiticbasalts, rhyolites, and porphyries, also with _Hf values of 6•1,associated with a volcanogenic massive sulphide deposit andapparently formed by differentiation of mantle-derived basalticmelts at shallow levels in an extensional back-arc setting. The second magmatic suite, formed between 2702 and 2693 Ma,comprises late orogenic plutons and batholiths of dioritic todominantly granodioritic composition. The characteristics ofthese intrusions are consistent with a process combining meltingof a metasomatized mantle source and subsequent fractional crystallizationof the derived magmas at shallow depths. However, most of thestudied occurrences show evidence of crustal contamination throughvarious combinations of assimilation of lower-crustal material,assimilation of underthrust sedimentary rocks, and contaminationby wall rock materials during the latest stages in the emplacementof the plutons. The involvement of crustal material is indicatedby the presence of zircon xenocrysts and by _Hf values rangingfrom 1•4 to 4•4. Only one intrusion, with an _Hf valueof 5•0 and no xenocrystic zircon, appears to have escapedwidespread contamination, perhaps because the ascent of itsmagma was facilitated by a crustal-scale fracture system.     

Geochemical and Isotopic Heterogeneities along an Island Arc-Spreading Ridge Intersection: Evidence from the Lewis Hills, Bay of Islands Ophiolite, Newfoundland

This study focuses on the origin of magma heterogeneity andthe genesis of refractory, boninite-type magmas along an arc–ridgeintersection, exposed in the Lewis Hills (Bay of Islands Ophiolite).The Lewis Hills contain the fossil fracture zone contact betweena split island arc and its related marginal oceanic basin. Threetypes of intrusions, which are closely related to this narrowtectonic boundary, have been investigated. Parental melts inequilibrium with the ultramafic cumulates of the PyroxeniteSuite are inferred to have high MgO contents and low Al₂O₃,Na₂O and TiO₂ contents. The trace element signatures of thesePyroxenite Suite parental melts indicate a re-enriched, highlydepleted source with 0·1 x mid-ocean ridge basalt (MORB)abundances of the heavy rare earth elements (HREE). Initial_Nd values of the Pyroxenite Suite range from -1·5 to+0·6, which overlap those observed for the island arc.Furthermore, the Pyroxenite Suite parental melts bear strongsimilarities to boninite-type equilibrium melts from islandarc-related pyroxenitic dykes and harzburgites. Basaltic dykessplit into two groups. Group I dykes have 0·6 x MORBabundances of the HREE, and initial _Nd values ranging from +5·4to +7·5. Thus, they have a strong geochemical affinitywith basalts derived from the marginal basin spreading ridge.Group II dykes have comparatively lower trace element abundances(0·3 x MORB abundances of HREE), and slightly lower initial_Nd values (+5·4 to +5·9). The geochemical characteristicsof the Group II dykes are transitional between those of GroupI dykes and the Pyroxenite Suite parental melts. Cumulates fromthe Late Intrusion Suite are similarly transitional, with _Ndvalues ranging from +2·9 to +4·6. We suggest thatthe magma heterogeneity observed in the Lewis Hills is due tothe involvement of two compositionally distinct mantle sources,which are the sub-island lithospheric mantle and the asthenosphericmarginal basin mantle. It is likely that the refractory, boninite-typeparental melts of the Pyroxenite Suite result from remeltingof the sub-arc lithospheric mantle at an arc–ridge intersection.Furthermore, it is suggested that the thermal-dynamic conditionsof the transtensional transform fault have provided the prerequisitefor generating magma heterogeneity, as a result of mixing relationshipsbetween arc-related and marginal basin-related magmas. KEY WORDS: Bay of Islands ophiolite; transform (arc)–ridge intersection; boninites; rare earth elements, Nd isotopes     

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