Oxygen and hydrogen isotope studies of contact metamorphism in the Santa Rosa Range,Nevada and other areas

The O¹⁸/O¹⁶ and D/H ratios have been determined for rocks and coexisting minerals from several granitic plutons and their contact metamorphic aureoles in the Santa Rosa Range, Nevada, and the Eldora area, Colorado, with emphasis on pelitic rocks. A consistent order of O¹⁸/O¹⁶ and D/H enrichment in coexisting minerals, and a correlation between isotopic fractionations among coexisting mineral pairs are commonly observed, suggesting that mineral assemblages tend to approach isotopic equilibrium during contact metamorphism. In certain cases, a systematic decrease is observed in the oxygen isotopic fractionations of mineral pairs as one approaches the intrusive contacts. Isotopic temperatures generally show good agreement with heat flow considerations. Based on the experimentally determined quartz-muscovite O¹⁸/O¹⁶ fractionation calibration curve, temperatures are estimated to be 525 to 625° C at the contacts of the granitic stocks studied.Small-scale oxygen isotope exchange effects between intrusive and country rock are observed over distances of 0.5 to 3 feet on both sides of the contacts; the isotopic gradients are typically 2 to 3 per mil per foot. The degree of oxygen isotopic exchange is essentially identical for different coexisting minerals. This presumably occurred through a diffusion-controlled recrystallization process. The size of the oxygen isotope equilibrium system in the small-scale exchanged zones varies from about 1.5 to 30 cm. A xenolith and a re-entrant of country rock projecting into an intrusive have both undergone much more extensive isotopic exchange (to hundreds of feet); they also show higher isotopic temperatures than the rocks in the aureole. The marginal portions of most plutons have unusually high O¹⁸/O¹⁶ ratios compared to normal igneous rocks, presumably due to large-scale isotopic exchange with metasedimentary country rocks when the igneous rocks were essentially in a molten state. The isotopic data suggest that outward horizontal movement of H₂O into the contact metamorphic aureoles is very minor, but upward movement of H₂O is important. Also, direct influx and absorption of H₂O from the country rock appears to have occurred in certain intrusive stocks. The D/H ratios of biotites in the contact metamorphic rocks and their associated intrusions show a geographic correlation that is similar to that shown by the D/H ratios of meteoric surface waters, perhaps indicating that meteoric waters were present in the rocks during crystallization of the biotites.Except in the exchanged zones, the O¹⁸/O¹⁶ ratios of pelitic rocks do not change appreciably during contact metamorphism, even in the cordierite and sillimanite grades; this is in contrast to regional metamorphic rocks which commonly decrease in O¹⁸ with increasing grade. Thus, contact metamorphic rocks generally do not exchange with large quantities of igneous H₂O, but regional metamorphic rocks appear to have done so.Publications of the Division of Geological Sciences, California Institute of Technology, Contribution No. 1565.     

Oxygen isotope study of metamorphic and granitic rocks of the Yanai district in the Ryoke belt,Japan

¹⁸O/¹⁶O ratios have been obtained for 134 whole-rocks and minerals from metamorphic and granitic rocks of the Yanai district in the Ryoke belt, Southwest Japan. The ¹⁸O/¹⁶O ratios of pelitic rocks of the marginal metamorphic zone decrease progressively with increasing metamorphic grade. In the gneiss-granite complex (zone of migmatite [1]), the most characteristic feature of the rocks is that oxygen isotopic homogenization proceeds on both local and regional scales in parallel with “granitization” or chemical homogenization. Granitic rocks of various origin are fairly uniform in isotopic composition with δ ¹⁸O of quartz of 12 to 14‰ (SMOW) and δ ¹⁸O of biotite of 7 to 9‰ and are about 3 to 4‰ enriched in ¹⁸O compared to other Cretaceous granites of non-metamorphic terranes in Japan. The high ¹⁸O/¹⁶O ratios of granitic rocks of this district were discussed in relation to the ¹⁸O-depletion in metasediments. Oxygen isotopic fractionations among coexisting minerals from various rock-types of the gneiss-granite complex indicate that these minerals were formed under near isotopic equilibrium at a temperature of about 600 to 700° C. Some abnormal fractionations of quartz-biotite pairs also were obtained for rocks which had undergone a progressive ¹⁸O-depletion or ¹⁸O-enrichment. This is due to high resistivity of quartz and contrastive susceptibility of biotite to isotopic exchange during metamorphism and “granitization”.     

Isotopic and Geochemical Investigation of the Chilwa Island Carbonatite Complex, Malawi: Evidence for a Depleted Mantle Source Region, Liquid Immiscibility, and Open-System Behaviour

Initial Nd, Pb, and Sr isotopic data from carbonatites and associatedintrusive silica-undersaturated rocks from the early Jurassic,Chilwa Island complex, located in southern Malawi, central Africa,suggest melt derivation from a Rb/Sr- and Nd/Sm-depleted butTh/Pb- and U/Pb-enriched mantle source. Initial ¹⁴³Nd/¹⁴⁴Nd(0.51265–0.51270) isotope ratios from the Chilwa Islandcarbonatites are relatively constant, but their initial ⁸⁷Sr/⁸⁶Sr(0.70319–0.70361) ratios are variable. The ¹⁸O_smow (9.53–14.15%0)and ¹³C_PDB (–3.27 to –1.50%0) isotope ratios ofthe carbonates are enriched relative to the range of mantlevalues, and there is a negative correlation between ¹⁸O andSr isotope ratios. The variations in Sr, C, and O isotopic ratiosfrom the carbonatites suggest secondary processes, such as interactionwith meteoric groundwater during late-stage carbonatite activity.The initial ¹⁴³Nd/¹⁴⁴Nd (0.51246 0.51269) and initial ⁸⁷Sr/⁸⁶Sr(0.70344–0.70383) isotope ratios from the intrusive silicaterocks are more variable, and the Sr more radiogenic than thosefrom the carbonatites. Most of the Pb isotope data from Chilwa Island plot to the rightof the geochron and close to the oceanic regression line definedby MORBs and OIBs. Initial Pb isotopic ratios from both carbonatites(²⁰⁷Pb/²⁰⁴Pb 15.63–15.71; ²⁰⁶Pb/²⁰⁴Pb 19.13–19.78)and silicate rocks (²⁰⁷Pb/²⁰⁴Pb 15.61–15.72; ²⁰⁶Pb/²⁰⁴Pb18.18–20.12) show pronounced variations, and form twogroups in Pb-Pb plots. The isotopic variations shown by Nd, Pb, and Sr for the ChilwaIsland carbonatites and intrusive silicates suggest that thesemelts underwent different evolutionary histories. The chemicaldata, including isotopic ratios, from the carbonatites and olivinenephelinites are consistent with magmatic differentiation ofa carbonated-nephelinite magma. A model is proposed in whichdifferentiation of the carbonatite magma was accompanied byfenitization (metasomatic alteration) of the country rocks bycarbonatite-derived fluids, and subsequent alteration of thecarbonatite by hydrothermal activity. The chemical and isotopicdata from the non-nephelinitic intrusive silicate rocks reveala more complex evolutionary history, involving either selectivebinary mixing of lower-crustal granulites and a nephelinitemagma, or incremental batch melting of a depleted source andsubsequent crustal contamination.     

Hydrogen and oxygen isotope evidence for fluid–rock interactions in the Menderes massif, western Turkey

The Menderes Massif comprises an inner crystalline core with gneissic rocks and an outer surrounding schist belt with predominantly metasedimentary rocks. Both units have a complex metamorphic history including a late Alpine overprint. Temperatures inferred from oxygen isotope compositions of coexisting minerals increase from 420 to 600°C from the rim to the center. More positive '¹⁸O values in all minerals from the schist belt may reflect a higher abundance of sedimentary precursor material, whereas biotites and muscovites in core and rim are indistinguishable in hydrogen isotope composition. 'D values of muscovites range from -35 to -60‰, whereas 'D values of biotites range from -65 to -125‰, indicating normal values for muscovite but anomalously negative values for some biotites. For muscovite the trend can be interpreted in terms of increasing loss of water with rising metamorphic temperature. For biotite the 'D values decrease with increasing H₂O content and decreasing Na₂O+K₂O content, which provides evidence for alteration processes or exchange of K and Na with water from interlayers of biotite forming hydro-biotite. The data suggest isotopic resetting of pre-Alpine characteristics during Alpine metamorphism. The hydrogen isotope composition of biotite was later disturbed, probably during extensional neotectonic movements in this region, as this allowed infiltration of and exchange with D-depleted meteoric water; however, the muscovites retained its Alpine characteristics.     

Geochemistry and Intrusive History of the Ashland Pluton, Klamath Mountains, California and Oregon

The Ashland pluton is a calc-alkaline plutonic complex thatintruded the western Paleozoic and Triassic belt of the KlamathMountains in late Middle Jurassic time. The pluton comprisesa series of compositionally distinct magma pulses. The oldestrocks are hornblende gabbro and two-pyroxene quartz gabbro withinitial ⁸⁷Sr/⁸⁶Sr = 0{dot}7044, ¹⁸O = 8{dot}7%, and REE patternswith chondrite normalized La/Lu = 7. These units were followedby a suite of tonalitic rocks (La_N/Lu_N = 7) and then by a suiteof K₂O- and P₂O₅ rocks of quartz monzodioritic affinity (La_N/Lu_N= 13–21; La_N/Sm_N = 2{dot}4–3{dot}) The quartz monzodioriticrocks were then intruded by biotite granodiorite and granitewith lower REE abundances but more fractionated LREE(La_N/Lu_N= 13–19; La_N/Sm_N = 4{dot}3–6 and they, in turn,were host to dikes and bosses of hornblende diorite. The latestintrusive activity consisted of aplitic and granitic dikes.Combined phase equilibria and mineral composition data, indicateemplacement conditions of approximately P_total = 2{dot}3kb,P_H2O between 1{dot}5 and 2{dot}2 kb, and f_O2 between the nickel-nickeloxide and hematite-magnetite buffers. Successive pulses of magma display increasing SiO₂ togetherwith increasing ¹⁸O and decreasing initial ⁸⁷Sr/⁸⁶Sr. The isotopicdata are consistent with either (1) combined fractional crystallizationof andesitic magma and concurrent assimilation of crustal materialcharacterized by low Sr₁ and high (¹⁸O or, more probably, (2)a series of partial melting events in which sources were successivelyless radiogenic but richer in ¹⁸O Each intrusive stage displaysevidence for some degree of crystal accumulation and/or fractionalcrystallization but neither process adequately accounts fortheir compositional differences. Consequently, each stage appearsto represent a distinct partial melting or assimilation event. The P₂O₅-rich nature of the quartz monzodiorite suite suggestsaccumulation of apatite. However, the suite contains abundantmafic microgranitoid enclaves and most apatite in the suiteis acicular. These observations suggest that magma mixing affectedthe compositional variation of the quartz monzodiorite suite.Mass balance calculations are consistent with a simple mixingprocess in which P₂O₅-rich alkalic basalt magma (representedby the mafic microgranitoid enclaves) was combined with a crystal-poorfelsic magma (represented by the tonalite suite), yielding aquartz monzodioritic magma that then underwent differentiationby crystal fractionation and accumulation.     

Fractionation of carbon and oxygen isotopes and magnesium between coexisting metamorphic calcite and dolomite

Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C $$ \begin{gathered} 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.45 (10^6 T^{ - 2} ) - 0.40 \hfill \\ 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.18 (10^6 T^{ - 2} ) + 0.17. \hfill \\ \end{gathered} $$ These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C¹³ partial exchange experiments of this study. Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO _D ¹⁸ –δO _Ct ¹⁸ values. The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C¹³/C¹² ratios in Grenville and Vermont marbles and O¹⁸/O¹⁶ ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O¹⁸(δO¹⁸=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange. Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O¹⁸ by about 4.9‰ and in C¹³ by about 2.4‰.     

Sauerstoff-Isotopenuntersuchungen an Mineralen eines metamorphen Profils der Hohen Tauern, Österreich

Oxygen isotope analyses on minerals of a metamorphic profile from Hohe Tauern, Austria indicate that the oxygen isotopes of the coexisting minerals quartz, garnet, and biotite have been reequilibrated during alpidic metamorphism. The K/Ar-ages of these biotites are in the range of 20–30 my. Metamorphic temperatures can be calculated from the quartz-biotite and quartz-garnet isotopic fractionations. The metamorphic temperature in the northern part of the region under investigation is 440° C and increases in direction to Tauernhauptkamm to about 600° C. Indicated by petrographic investigations, two samples from this area show no remarkable metamorphic influence. K/Ar-determinations on hornblendes and biotites yielded variscan ages.The isotopic temperatures of these samples, calculated by the oxygen isotope fractionations of quartz-biotite, quartz-magnetite, and feldspar-magnetite are equal within the limits of instrumental error and represent the crystallisation temperature of a granodioritic magma of 660–670° C.     

Metamorphism and Structure of Penfold Creek Area, near Quesnel Lake, British Columbia

The Quesnel Lake area lies within the Omineca Crystalline Belt,and is underlain by the northern extremity of the Shuswap MetamorphicComplex. Closely spaced and steeply dipping isograds mark themargins of the metamorphic belt. In the Penfold Creek area onlyone and one-half miles separate the biotite and sillimaniteisograds. Related to this sharp increase in metamorphic gradethere is a marked change in the fold style. In the chloritezone are similar folds, showing a strong axial-plane cleavage,and tight refolded isoclines dominate in the sillimanite zone.Three periods of deformation and two periods of prograde metamorphismhave been recognized, with the first metamorphic period beingassociated with Phase 2 deformation and the second being post-Phase2. Regression analysis of possible mineral reactions in these rocksshows that they formed under conditions of a gradient in temperatureand possibly H₂O activity, and that most of the assemblages,although containing many phases, have at least two degrees offreedom. Thermodynamic analysis of mineral equilibria indicatesthat equilibrium was closely approached between solid solutionsinvolving garnet, plagioclase, biotite, white mica, and staurolitein the presence of Al₂SiO₅, quartz, and H₂O. The conditionsof metamorphism of rocks containing Al₂SiO₅ are estimated tobe 7000 ± 1500 bars, 680 ± 30 °C, activityof H₂O = 0.80 (approx.). Partial melting did not occur becauseof the reduced activity of H₂O. ^*Present address: Overseas Division, Institute of Geological Sciences, 5 Princes Gate, London SW7, England.     

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     

Transition from the Zeolite to Prehnite-Pumpellyite Facies in the Karmutsen Metabasites, Vancouver Island, British Columbia

The upper Triassic Karmutsen metabasites from northeast VancouverIsland, B.C., are thermally metamorphosed by the intrusion ofthe Coast Range Batholith. The amygdaloidal metabasites developedin the outer portion of the contact aureole show a progressivemetamorphism from zeolite to prehnite-pumpellyite facies. Thesize of an equilibrium domain is extremely small for these metabasites,and the individual amygdule assemblages are assumed to be inequilibrium. Two major calcite-free assemblages (+chlorite+quartz)are characteristic: (i) laumontite+pumpellyite+epidote in thezeolite facies and (ii) prehnite+pumpellyite+epidote in theprehnite-pumpellyite facies. The assemblages and compositionsof Ca-Al silicates are chemographically and theoretically interpretedon the basis of the predicted P-T grid for the model basalticsystem, CaO-MgO-A1₂O₃-Fe₂O₃-SiO₂-H₂O. The results indicate:(1) local equilibrium has been approached in mineral assemblagesand compositions; (2) the X_Fe³⁺ values in the coexisting Ca-Alsilicates decrease from epidote, through pumpellyite to prehnite;(3) with increasing metamorphic grade, the Fe³⁺ contents ofepidotes in reaction assemblages decrease in the zeolite facies,then increase in the prehnite-pumpellyite facies rocks. Suchvariations in the assemblages and mineral compositions are controlledby a sequence of continuous and discontinuous reactions, andallow delineation of T-X_Fe³⁺ relations at constant pressure.The transition from the zeolite to prehnite-pumpellyite faciesof the Karmutsen metabasites is defined by a discontinuous reaction:0·18 laumontite+pumpellyite+0·15 quartz = 1·31prehnite+ 0·78 epidote+0·2 chlorite+ 1·72H₂O, where the X_Fe³⁺ values of prehnite, pumpellyite and epidoteare 0·03, 0·10 and 0·18, respectively.These values together with available thermodynamic data andour preliminary experimental data are used to calculate theP-T condition for the discontinuous reaction as P = 1·1±0·5 kb and T = 190±30°C. The effectsof pressure on the upper stability of the zeolite facies assemblagesare discussed utilizing T-X_Fe³⁺ diagrams. The stability of thelaumontite-bearing assemblages for the zeolite facies metamorphismof basaltic rocks may be defined by either continuous or discontinuousreactions depending on the imposed metamorphic field gradient.Hence, the zeolite and prehnite-pumpellyite facies transitionboundary is multivariant.     

Chemistry of Kornerupine and Associated Minerals, a Wet Chemical, Ion Microprobe, and X-Ray Study Emphasizing Li, Be, B and F Contents

Kornerupine and associated minerals in 31 samples of high-graderocks relatively rich in Al and Mg were analysed by wet chemistry,ion microprobe mass analyser, electron microprobe and X-raypowder diffraction. For 11 samples of kornerupine and threesamples of biotite (F only) analysed by both wet chemical andion microprobe methods, the best agreement was obtained forB₂O₃, whereas the ion microprobe Li₂O values were systematicallysomewhat higher than the wet chemical values. The wet chemicalmethods give Li₂O=0–0?19 wt.%; BeO=0–0?032 wt.%;B₂O₃=0–4?01 wt.%; and F=0?07–0?77 wt.% in kornerupine,whereas ion microprobe analyses on other kornerupines give valuesup to 0?35 wt.% Li₂O, O066 wt.% BeO, and 4?72 wt.% B₂O₃. Thesum B+Al+Fe³⁺+Cr is close to 6?9 atoms per 22 (O, OH, F) or21?5 (O) in kornerupine. In general, Li/Fe ratios decrease as follows: kornerupine ?sapphirinebiotite> Crd (Na<0?03 per 18 oxygens)>tourmaline, garnet,orthopyroxene. However, for cordierite with Na>004, Li/Fedecreases as follows: cordierite>kornerupine. Sapphirineand sillimanite are the only associated minerals to incorporatesignificant boron (0?1–0?85 wt.% B₂O₃) and then only whenthe single site for B in kornerupine is approaching capacity.Sillimanite B₂O₃ contents increase regularly with kornerupineF. Fractionation of fluorine increases as follows: kornerupine<biotite<tourmaline,and K^krn-BtD=(F/OH)^Krn/(F/(OH)^Bt (assuming ideal anion composition)increases with biotite Ti. Kornerupine B₂O₃ content is a measureof B₂O₃ activity in associated metamorphic fluid, whereas sillimaniteB₂O₃ content increases with temperature, exceeding 0?4 wt.%whenT=900?C at very low water activities. New data on 11 kornerupines and literature data indicate thatthe unit cell parameters a, c, and V decrease with increasingB content and b, c, and V increase with increasing Fe³⁺ content.In Fe³⁺-poor kornerupines, b increases with Mg and with (Mg+ Fe²⁺) but the effect of Mg on b via the substitution ^VIMg+^IVSi=^VIAl+^IVAloverwhelms the effect of Fe²⁺=Mg substitution.     

Pumpellyite-Actinolite Facies Schists of the Taveyanne Formation near Lo?che, Valais, Switzerland

Electron microprobe analyses are presented for new-formed mineralsfrom a small exposure of semi-schistose Taveyanne Formationof the pumpellyite-actinolite facies near Lo?che, Valais. Comparisonsare drawn with minerals of other low-grade metamorphic areas,especially in southern New Zealand. Sphene shows considerablesubstitution of Ca(Al,Fe)SiO₄(OH) for CaTiSiO₅. Epidotes aresharply divided into early pistacitic (Ps = 0.28–0.37)and later clinozoisitic varieties (Ps = 0.11–0.19). Pumpellyitesrange from pumpellyite-(Fe) to pumpellyite-(Al) and are generallyless Fe-rich than those of zeolite and prehnite-pumpellyitefacies. Pumpellyite inclusions in albitized plagioclase areparticularly low in Mg. Actinolites are low in A1₂O₃, TiO₂,and Na₂O, essentially identical compositions being nucleatedon detrital augite, hornblende, and in the matrix. Phengitesare also extremely low in Na₂O and TiO₂. Chlorites are ripidolites.Albitized clastic plagioclase has the composition An0.7–1.6and albite in clinozoisite-calcite-albite-phengite-chloriteveins An2.1–2.3. Calcites carry minor Mn > Fe ? Mg.New-formed iron oxides are absent, whereas pyrrhotite and minorpyrite occur in one rock, buffering fs₂ and indicating low fo₂. Ratios Mg: Fe^* (Fe^* = total Fe) in coexisting chlorites andA1, Na-poor actinolites vary sympathetically both in the Lo?cheand southern New Zealand rocks here considered, giving K_D =(Mg/Fe^*) _actlnolIte/(Mg/Fe^*)_chlorle = 1.72. Mg/Fe^* ratios inpumpellyites tend to vary sympathetically with those of coexistingchlorites and actinolites but are more variable. Substitutionof (Fe, Mg)Si for A1₂ in phengitic micas and chlorites variessympathetically in the same suites between mafic volcanic andmore pelitic extremes. Various minor elements also behave ina consistent fashion, indicating an encouraging tendency towardsequilibrium. Variable (though small) A1₂O₃ contents of actinolite,Fe: Al ratios in epidotes and pumpellyites, and Mg: Fe^* ratiosin phengites, even within a single grain, are evidence of short-rangedisequilibrium; metamorphic equilibration is evidently easierbetween some crystal structures and structural sites than betweenothers. In phase rule analysis of assemblages in such rocks it is commonlynecessary to treat Fe²O₃, FeO, and MgO as separate componentsand it may also be necessary to regard CO² as an inert componentand/or to interpret observed assemblages as of low variance.The presence of the Ca-Al silicates and sphene indicates verylow X_co2 in the metamorphic fluids in all rocks examined exceptan albite-chlorite-calcite-quartz-anatase assemblage. But higherAn in albites than in isofacial and in greenschist facies rocksof southern New Zealand can be ascribed to significantly higherXco₂ at Lo?che, especially in the veins, than in New Zealand. Pumpellyite and epidotes of the pumpellyite-actinolite faciestend to be lower in Fe and richer in Al than those of lowergrade facies. Important reactions include those of the formpumpellyite-(Fe³⁺)+chlorite+quartz+H₂=pumpellyite-(Al)+actinolite,and pumpellyite+chlorite+quartz- ‘epidote’+actinolite+water.Careful selection of pumpellyite and chlorite compositions isrequired for experimental and chemographic analysis of pumpellyitestability. In the absence of critical data, temperatures ofabout 250–350? and pressures of several kilobars are provisionallysuggested for the Lo?che metamorphism.     

Oxygen and hydrogen isotope geochemistry of gneisses associated with ultrahigh pressure eclogites at Shuanghe in the Dabie Mountains

The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ¹⁸O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ¹⁸O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The ¹⁸O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ¹⁸O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) ¹⁸O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998     

Melting and Thermal Reconstitution of Pelitic Xenoliths, Wehr Volcano, East Eifel, West Germany

Pelitic xenoliths derived from amphibolite grade basement rocksoccur within a Pleistocene, trachytic, pyroclastic unit of theWehr volcano, East Eifel, West Germany: With increasing temperatureand/or prolonged heating at high temperature, quartz-plagioclaseand micaceous layers of the xenoliths have undergone meltingto form buchites and thermal reconstitution by dehydration reactions,melting and crystallization to form restites respectively. Thexenoliths provide detailed evidence of melting, high temperaturedecomposition of minerals, nucleation and growth of new phasesand P-T-f_o2 conditions of contact metamorphism of basement rocksby the Wehr magma. Melting begins at quartz-oligoclase (An_17·3Ab_82·3Or_0·4-An_20·0Ab_78·1Or_1·9)grain boundaries in quartz-plagioclase rich layers and the amountof melting is controlled by H₂O and alkalis released duringdehydroxylation/oxidation of associated micas. Initially, glasscompositions are heterogeneous, but with increasing degreesof melting they become more homogeneous and are similar to S-typegranitic minimum melts with SiO₂ between 71 and 77 wt. per cent;A/(CNK) ratios of 1·2–1·4; Na₂O < 2·95and normative corundum contents of 1·9–4·0per cent. Near micas plagioclase melts by preferential dissolutionof the NaAlSi₃O₈ component accompanied by a simultaneous increasein CaAl²Si²O⁸ (up to 20 mol. per cent An higher than the bulkplagioclase composition) at the melting edge. With increasingtemperature the end product of fractional melting is the formationand persistence of refractory bytownite (An_78–80) in thosexenoliths where extensive melting has taken place. Initial stage decomposition of muscovite involves dehydroxylation(H₂O and alkali loss). At higher temperatures muscovite breaksdown to mullite, sillimanite, corundum, sanidine and a peraluminousmelt. Mullite (40–43 mol. per cent SiO₂) and sillimanite(49 mol. per cent SiO₂) are Fe₂O₃ and TiO₂ rich (up to 6·1–0·84and 3·6–0·24 wt. per cent respectively).Al-rich mullite (up to 77 wt. per cent Al₂O₃) occurs with corundumwhich has high Fe₂O₃ and TiO₂ (up to 6·9 and 2·1wt. per cent respectively). Annealing at high temperatures andreducing conditions results in the exsolution of mullite fromsillimanite and ilmenite from corundum. Glass resulting fromthe melting of muscovite in the presence of quartz is peraluminous(A/(CNK) = 1·3) with SiO² contents of 66–69 percent and normative corundum of 4 per cent. Sanidine (An_1·9Ab_26·0Or_72·1-An_1·3Ab_15·9Or_82·9)crystallized from the melt. Dehydroxylation and oxidation of biotite results in a decreaseof K₂O from 8·6 to less than 1 wt. per cent and oxidetotals (less H₂O + contents) from 96·5 to 88·6,exsolution of Al-magnetite, and a decrease in the Fe/(Fe + Mg)ratio from 0·41 to 0·17. Partial melting of biotitein the presence of quartz/plagioclase to pleonaste, Al-Ti magnetite,sanidine(An_2·0Ab_34·9Or63·1) and melt takesplace at higher temperatures. Glass in the vicinity of meltedbiotite is pale brown and highly peraluminous (A/CNK = 2·1)with up to 6 wt. per cent MgO+FeO_{(total iroq)} and up to 10 percent normative corundum. Near liquidus biotite with higher Al₂O₃and TiO₂ than partially melted biotite crystallized from themelt. Ti-rich biotites (up to 6 wt. per cent TiO₂) occur withinthe restite layers of thermally reconstituted xenoliths. Meltingof Ti-rich biotite and sillimanite in contact with the siliceousmelt of the buchite parts of xenoliths resulted in the formationof cordierite (100 Mg/(Mg+Fe+Mn) = 76·5–69·4),Al-Ti magnetite and sanidine, and development of cordierite/quartzintergrowths into the buchite melt. Growth of sanidine enclosedrelic Ca-plagioclase to form patchy intergrowths in the restitelayers. Cordierite (100 Mg/(Mg+Fe+Mn) = 64–69), quartz,sillimanite, mullite, magnetite and ilmenite, crystallized fromthe peraluminous buchite melt. Green-brown spinels of the pleonaste-magnetite series have awide compositional variation of (mol. per cent) FeAl₂O₄—66·6–45·0;MgAl₂O₄—53·0–18·7; Fe₃O₄—6·9–28·1;MnAl₂O₄—1·2–1·5; Fe₂TiO₄—0·6–6·2.Rims are generally enriched in the Fe₃O₄ component as a resultof oxidation. Compositions of ilmenite and magnetite (single,homogeneous and composite grains) are highly variable and resultfrom varying degrees of high temperature oxidation that is associatedwith dehydroxylation of micas and melting. Oxidation mainlyresults in increasing Fe³⁺, Al and decreasing Ti⁴⁺, Fe²⁺ inilmenite, and increasing Fe²⁺, Ti⁴⁺ and decreasing Fe³⁺ in associatedmagnetite. A higher degree of oxidation is reached with exsolutionof rutile from ilmenite and formation of titanhematite and withexsolution of pleonaste from magnetite. Ti-Al rich magnetite(5·1–7·5 and 8·5–13·5wt. per cent respectively) and ilmenite crystallized from meltsin buchitic parts of the xenoliths. Chemical and mineralogic evidence indicates that even with extensivemelting the primary compositions of individual layers in thexenoliths remained unmodified. Apparently the xenoliths didnot remain long enough at high temperatures for desilicationand enrichment in Al₂O₃, TiO₂, FeO, Fe₂O₃, and MgO that resultsby removal of a ‘granitic’ melt, and/or by interactionwith the magma, to occur. T °C-f_o2 values calculated from unoxidized magnetite/ilmenitegive temperatures ranging from 615–710°C for contactmetamorphism and the beginning of melting, and between 873 and1054°C for the crystallization of oxides and mullite/sillimanitefrom high temperature peraluminous melts. f_o2 values of metamorphismand melting were between the Ni-NiO and Fe₂O₃-Fe₃O₄ buffer curves.The relative abundance of xenolith types, geophysical evidenceand contact metamorphic mineralogy indicates that the xenolithswere derived from depths corresponding to between 2–3kb P_load = P_fluid. The xenoliths were erupted during the latestphreatomagmatic eruption from the Wehr volcano which resultedin vesiculation of melts in partially molten xenoliths causingfragmentation and disorientation of solid restite layers.     

Zonal distribution of oxygen isotope ratios in the Hiroshima granite complex,Southwest Japan

¹⁸O/¹⁶O ratios have been obtained for 99 minerals from rocks of the Hiroshima granite complex and adjacent Ryoke granites. Zonal distribution of oxygen isotopes is observed on a regional scale almost parallel to the extension of the Ryoke plutono-metamorphic belt, granites in or around the metamorphic belt being 2–3%₀ richer in ¹⁸O than those farther away from the belt. Isotopic fractionations among coexisting minerals indicate that isotopic zonation existed at a magmatic stage. The zonal enrichment of ¹⁸O in the granite magma in the Ryoke belt and its periphery is a result of isotopic interaction between country rocks and the magma through fluid media. Genetic relationship between granites of the Ryoke and Chugoku belts are discussed with regard to the geological situation of the former belt.     

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

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

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Oxygen and hydrogen isotope study of minerals from metapelitic rocks, staurolite to sillimanite zones, Mica Creek, British Columbia

Abstract Oxygen and hydrogen isotope analyses have been made of coexisting quartz, ilmenite, muscovite, and biotite from Late Precambrian metapelitic rocks, staurolite-kyanite to K-feldspar-muscovite-sillimanite zones, from Mica Creek, British Columbia. The δ¹⁸O and †D values of these minerals are generally uniform and do not decrease significantly with increasing metamorphic grade. This implies that there has not been significant infiltration of deep crustal, possibly magmatic, fluids into the metapelites that has been suggested for other high-grade metamorphic terranes. The uniformity of oxygen isotope compositions of the Mica Creek metapelite rocks may reflect isotopic uniformity in the sedimentary protolith rather than widespread exchange with an isotopically homogeneous metamorphic pore fluid.
Temperature estimates based upon ¹⁸O exchange thermometry for samples below the sillimanite zone are in reasonable agreement with the results of garnet-biotite Fe–Mg exchange thermometry. In the higher grade rocks, the oxygen isotope and garnet-biotite thermometry yield results which disagree by about 100°C. The highest temperatures recorded by oxygen isotope thermometry, 595°C, are at least 60°C below the minimum temperatures required by phase equilibria. These discrepancies appear to result from pervasive equilibrium retrograde exchange of oxygen isotopes between coexisting minerals. In addition, there are problems with calibration of garnet-biotite thermometry at higher temperatures. Retrograde oxygen isotope exchange may be a general characteristic of high-grade metamorphic rocks and oxygen isotope thermometry may not usually record peak metamorphic temperatures if they significantly exceed 600°C.     

Phase equilibrium and stable isotope constraints on the formation of metasomatic garnet-vesuvianite veins (SW Adamello,N Italy)

 Metasomatic garnet-vesuvianite veins occur within the contact metamorphic marble sequence of the Lower Triassic Prezzo formation in a narrow, 1–5 m wide zone along an intrusive marble-granodiorite contact at the southwestern border of the Tertiary Adamello batholith. The metasomatic mineral assemblage is comprised of garnet, vesuvianite, clinopyroxene, wollastonite, and pyrrhotite, which were precipitated from the vein-forming fluid in a preexisting calcite matrix at conditions of about 2800 bars and 630° C. The veins are enriched in silicon, aluminum, iron, magnesium, titanium and depleted in calcium with respect to the unaltered contact metamorphic marble. Graphite, which is present in the unaltered Prezzo Marble is absent in the veins. Irregularly shaped mineralogically distinct zones with different degrees of silicification can be distinguished within the veins. The isotopic compositions of calcite (cc) in the unaltered marble are about δ¹⁸O (SMOW; Standard mean Ocean Water)=21.0‰ and δ¹³C(PDB; Peedee belemnite)=0.0‰. They are reset to significantly lower values within the veins, where δ¹⁸O_cc is 15.0 to 16.0‰ and δ¹³C_cc is −4.5 to −3.5‰. The isotopic front coincides with an abrupt change in the microscopic texture of matrix carbonate which occurs at the sharp boundary between graphite-bearing and graphite-free material. Within the veins the oxygen isotope fractionation between calcite and garnet (gar) varies systematically with distance from highly silicified zones. The variations in Δ¹⁸O_cc-gar are as large as 2‰, on a millimeter scale, indicating garnet-calcite isotopic disequilibrium. Vein formation was due to the infiltration of a water rich fluid of magmatic provenance into the carbonate country rock along fractures. Removal of graphite from the wall rock by dissolution through the metasomatic fluid induced recrystallization of matrix calcite. Permeability was enhanced during calcite recrystallization facilitating material transport into the wall rock and metasomatic alteration. Vein garnet was precipitated in isotopic equilibrium with the metasomatic fluid. The isotopic composition of preexisting calcite was initially out of equilibrium with the vein-forming fluid and it was shifted towards equilibrium by surface-reaction controlled calcite-fluid isotopic exchange during calcite recrystallization. Due to the short lifetime of the metasomatic system, calcite-fluid isotopic equilibrium was generally not attained. Within the veins, oxygen and carbon transport was fast relative to mineral-fluid exchange of their isotopes and the geometry of the isotopic pattern is largely controlled by the kinetics of mineral-fluid exchange. Received: 16 June 1994/Accepted: 20 May 1995     

Low-O18 Igneous Rocks from the Intrusive Complexes of Skye, Mull, and Ardnamurchan, Western Scotland

Oxygen isotope analyses have been obtained on rocks and coexistingminerals from the Tertiary stocks, ring-dikes, and cone-sheetsin Ardnamurchan (18 samples), Skye (41 samples), and Mull (18samples); these include a few samples of the plateau basaltcountry rocks. Almost all of the rocks in the vicinity of thecentral ring complexes (within 2 mi. of an intrusive contact)are strongly depleted in O¹⁸ relative to ‘normal’igneous rocks from other areas. The rocks in Skye ( 150 sq.mi.) and Mull ( 150 sq. mi.) have suffered an overall O¹⁸ depletionof about 6 to 7 per mil, and those in Ardnamurchan ( 30 sq.mi.) about 3 to 6 per mil. These data indicate that very large hydrothermal convectionsystems involving heated low. O¹⁸ meteoric ground waters wereestablished in these areas at the time of igneous intrusion.The heated ground waters exchanged with the gabbros, granities,and basaltic lavas, locaclly lowering their O¹⁸/ O¹⁶ rationsby at least 12 per mil. Much, if not all, of this exchange occurredafter crystallization of a given igneous rock was essentiallycomplete, inasmuch as feldspars invariably have undergone muchmore depletion in O¹⁸ than has coexisting quartz or pyroxen.The meteoric-hydrothermal process and the presence of an aqueousgas phase may possibly be responsible for the widespread epidote-chloritealteration, the turbid or cloudy feldspars, the abundant feldspathicveins, the felsitic and granophyric textures, the miaroliticcavities, and much of the explosive volcanic activity and brecciationthat are found in these areas.