Metamorphism, Fluid Flow and Partial Melting in Pelitic Rocks from the Onawa Contact Aureole, Central Maine, USA

Field, petrologic and geochemical data were used to characterizefluid infiltration and partial melting during metamorphism ofpelitic rocks in the contact aureole of the Onawa pluton, centralMaine, USA. Mineral assemblages delineate five metamorphic zoneswithin the contact aureole: chlorite zone, andalusite–cordierite(a–c) zone, alkali feldspar zone, sillimanite zone andleucocratic-vein (l–v) zone. The sequence of observedmineral assemblages and mineral–fluid reactions calculatedby mass balance is similar to those observed in other contactaureoles. Pressure of contact metamorphism is 3 kbar, on thebasis of optimum geothermobarometry calculations. Metamorphictemperatures vary from 500C in the andalusite–cordieritezone to 65OC in the leucocratic-vein zone. Data from fieldobservations, mineral textures, observed reaction stoichiometry,geothermometry and major-element geochemistry suggest that theleucocratic veins of the l-v zone represent crystallized, partialmelts. Two overall calculated mineral reactions are responsiblefor vein formation: which can be modeled as combinations of two NKFMTASH meltingreactions: Progress of (M1) and (M2) was measured in eight samples, andreaction (M1) is the dominant melt-forming reaction in all samples.Partial melting (and vein formation) was therefore driven byinfiltration of the l-v zone by H²O-rich fluids. Calculatedtime-integrated fluid fluxes for l-v zone samples range from09 10⁴ to 31 10⁴ mol/cm², and flow was in the directionof increasing temperature. KEY WORDS: pelites; contact metamorphism; fluid infiltration; partial melting; Onawa Pluton; Maine; USA ^*Corresponding author. Telephone:(516) 632–8192. Fax (516)632–8240 e-mail: gsymmes{at}ccmail.sunysb.edu     

Immiscibility in Ca-amphiboles

The literature data of nine different occurrences of coexistingmineral pairs of Ca-amphibole have been studied and the bulkvectors, spanning the miscibility gap, derived. The additivecomponent is always impure Mg-tremolite accompanied by someglaucophane and cummingtonite component. The four major exchangecomponents required to describe the compositional variationin coexisting mineral pairs are the edenite (ED), tschermak's(TS), FeMg_–1 and Fe³⁺-tschermak's (FeTs) vector. Trivalentiron is postulated on the basis of excess charges in the bulkvector the size of which coincides with residuals in Al^tet,–Si, Fe and –Mg. The four cations have equal sizes,forming the vector Fe³⁺ Al^tet Mg_–1Si_–1. This distributionscheme is consistent for all the different occurrences and setsthe basis for a comparison. Deviations from the scheme wouldradically complicate the proposed exchange pattern. The ratioTS:ED in most mineral samples fluctuates between one and two.Projection of the data points in the vector space TS–EDonto the line 1ED: 2TS (Tr–Hbl) or 1ED:1TS (Tr–Prg)provides the projected tremolite content (= 1–X_Hbl or = 1–X_prg). This parameter,applied to coexisting pairs, and plotted against the ratio Mg/(Mg+ Fe) shows some characteristic features about the miscibilitygap. In the Mg-pure system the solvus is almost symmetric andlocated in the temperature range between 800 and 870C. Smallamounts (0.10 pfu) of Fe²⁺ in the M(4) -sites and replacingCa have a dramatic effect, forcing the solvus to much lowertemperatures of 650C. An increase in the ratio Fe/(Fe + Mg)causes a shift of the solvus towards more tremolitic compositionswith temperatures 500–650C. The maximum asymmetry ofthe solvus is reached where the Al-poor member (tremolite) hasa composition of =1.0 and Mg/ (Mg + Fe) 0.6. The corresponding Al-rich member has =0.5 and Mg/ (Mg + Fe) 0.4. An anomalyof the solous is observed at Mg/ (Mg + Fe)=0.8. It manifestsas a kind of highly asymmetric ‘sub-gap’ in thetremolite-rich composition range. This is explained by the partitioningof Fe²⁺ into the single M(3) -site and is characterized by athermal hump to 650–700C. KEY WORDS: tremolite; hornblende; pargasite; immiscibility; solous     

An Experimental Study of Fe-Al Solubility in the System Corundum-Hematite up to 40 kbar and 1300{degrees}C

The mutual solubility in the system corundum–hematite[-(Al, Fe³⁺)₂O₃] was investigated experimentally using bothsynthetic and natural materials. Mixtures of -Al₂O₃ and -Fe₂O₃(weight ratios of 8:2 and 10:1) were used as starting materialsfor synthesis experiments in air at 800–1300°C withrun times of 7–34 days. Experiments at 8–40 kbarand 490–1100°C were performed in a piston-cylinderapparatus (run times of 0·8–7·4 days) usinga natural diasporite consisting of 60–70 vol. % diasporeand 20–30 vol. % Ti-hematite. During the diasporite–corunditetransformation, the FeTiO₃ component (12–18 mol %) ofTi-hematite only slightly increased, implying that oxygen fugacitywas maintained at high values. Run products were studied byelectron microprobe and X-ray diffraction (Rietveld) techniques.An essentially linear volume of mixing exists in the solid solutionwith a slight positive deviation at the hematite side. Up to1000°C, corundum contains <4 mol % Fe₂O₃ and hematite<10 mol % Al₂O₃; at 1200°C these amounts increase to9·3 and 17·0 mol %, respectively. At 1300°Chematite was no longer stable and coexists with the orthorhombic phase . The present results agree with corundum (solvus) compositions obtained inprevious studies but indicate a larger solubility of Al in hematite.The miscibility gap in the solution can be modelled with anasymmetric Margules equation with interaction parameters (2uncertainties): ; ; ; . Application of the corundum–hematite solution as a solvus geothermometer is limited because of thescarcity of suitable rock compositions. KEY WORDS: corundum; hematite; corundum–hematite miscibility gap; experimental study; Margules model; metabauxite     

Recalibration of the Garnet-Muscovite (GM) Geothermometer and the Garnet-Muscovite-Plagioclase-Quartz (GMPQ) Geobarometer for Metapelitic Assemblages

The garnet–muscovite (GM) geothermometer and the garnet–muscovite–plagioclase–quartz(GMPQ) geobarometer have been simultaneously calibrated underconditions of T = 450–760°C and P = 0·8–11·1kbar, using a large number of metapelitic samples in the compositionalranges = 0·53–0·81, = 0·05–0·24, = 0·03–0·23 in garnet, = 0·17–0·74 in plagioclase, and Fe = 0·04–0·16, Mg =0·04–0·13, Al^VI = 1·74–1·96in muscovite on the basis of 11 oxygens. The resulting GM thermometeryielded similar temperature estimates (mostly within ±50°C)to that of the garnet–biotite thermometer, and successfullydiscerned the expected systematic temperature change of progradesequences, thermal contact zones and an inverted metamorphiczone. The resulting GMPQ barometer yielded similar pressureestimates (mostly within ±1·0 kbar) to the garnet–aluminumsilicate–plagioclase–quartz (GASP) barometer andplaced the aluminosilicate-bearing samples in the appropriatealuminosilicate stability fields. Application of the GMPQ barometerto thermal contact aureoles or rocks within limited geographicalareas confirmed the expected constant pressures that shouldexist in these settings. The random errors of the GM thermometerand the GMPQ barometer are estimated to be ±16°Cand ±1·5 kbar, respectively. When biotite or aluminosilicateis absent in metapelites, metamorphic P–T conditions maybe determined by simultaneously applying the GM thermometerand the GMPQ barometer. KEY WORDS: application; calibration; geobarometer; geothermometer; metapelite     

Fluid--Rock Interaction during Low-Pressure Polymetamorphism of the Reynolds Range Group, Central Australia

Marbles and metapelites from the Reynolds Range Group (centralAustralia) were regionally metamorphosed at low pressure duringM₂ at 1.6 Ga, M₂ ranged in grade from greenschist to granulitefacies along the length of the Reynolds Range, and overprinted1.78 Ga granites and their contact aureoles in the ReynoldsRange Group metasediments. At all M₂ grades the marbles andmetapelites have highly variable oxygen isotope ratios [marbles:¹⁸O(carb) 14–20%; metapelites: ¹⁸O 6–14%). Similarly, 1.78 Ga granites have highly variable oxygen isotope ratios(¹⁸O 5–13%), with the lowest values occurring at thegranite margins. In all rock types, the lowest oxygen isotopevalues are consistent with the infiltration of channelled magmaticand/or meteoric fluids. The variable lowering of oxygen isotopevalues resulted from pre-M₂ contact metamorphism and fluid—rockinteraction around the 1.78 Ga granites. In contrast, mineralassemblages in the marbles define a trend of increasing X_CO2with increasing grade from <0.05 (greenschist facies) to0.7–1.0 (granulite facies). This, together with the lackof regionally systematic resetting of oxygen isotope ratios,implies that there was little fluid—rock interaction duringprograde regional metamorphism. KEY WORDS: low pressure; polymetamorphism; fluids; stable isotopes; petrology ^*Corresponding author Fax: 61–3–94791272. e-mail: geoisb{at}lure.latrobe.edu.au     

Oxygen and Hydrogen Isotope Geochemistry of the Mourne Mountains Tertiary Granites, Northern Ireland

An oxygen and hydrogen isotopic study of minerals and wholerocks from the granites of the Mourne Mountains Tertiary complex,and related rocks, shows that whereas a significant circulationof meteoric water was associated with the complex, it had onlyminor and localized effects on the granites themselves. TheSilurian slate and greywacke country rocks, which would havehad ¹⁸O_(SMOW) values of +10 to +20 before the Tertiary igneousevents, have been depicted ¹⁸O to values of –40 to –05Tertiary acid minor intrusions outside the main granite massesare also ¹⁸O depleted. ^l8O whole-rock data on the granites showa range of +6.0 to +9.5, and include values significantly higherthan most of those obtained for the granites of the Tertiarycentral complexes of Skye, Mull, and Ardnamurchan. Many of thelowest whole-rock ¹⁸O values are found in samples where theminerals are not in isotopic equilibrium. The mineral oxygenisotopic data can be explained in terms of localized interactionwith meteoric water, resulting in preferential ¹⁸O depletionin feldspar(s) and biotite, with quartz being much less affected.The granites all show low values of D_(SMOW) for biotite andamphibole separates (–137 to –104). The lowest valuesoccur close to the margins of the plutons, near internal contactsor near greisen localities, and these probably reflect limitedinteraction with meteoric water. The higher D values are fromsamples which show evidence of chloritization. This processappears to have occurred both during interaction with meteoricwater, and also during autometasomatism by an exsolved magmaticfluid in other parts of the plutons, including central locationswhere there is little or no evidence for the penetration ofmeteoric water. Granite samples which exhibit near-equilibriumoxygen isotope fractionations for constituent minerals are characterizedby magmatic O-isotopic compositions. The G2 granite, the largestpluton of the eastern centre, has a magmatic ¹⁸O_(SMOW) valueof {small tilde}+95; intrusions G3 (eastern centre) and G4(western centre) both have ¹⁸O_(SMOW) values of {small tilde}+90.The other two main intrusive phases have distinctly lower ¹⁸O_(SMOW)values: {small tilde}+75 for Gl (the least fractionated graniteof the Mourne Mountains central complex), and from +75 to +85for G5. The oxygen isotopic data rule out simple partial meltingof the country rocks as the origin of the granites and alsopreclude an origin by closed-system fractional crystallizationof basaltic magma typical of that represented by Tertiary basicigneous rocks of the region. ^* Present address: NERC Isotope Geosciences Laboratory, Keyworth, Nottingham BG12 5GG, UK Present address: School of Engineering Technology, Georgian College, Barrie, Ontario, L4M 3X9, Canada     

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     

Calibration and Applications of Spinel Equilibria in the System FeO-Al2O3-SiO2

A new thermobarometer, based on the equilibrium: has been calibrated with experiments carried out in the piston-cylinderapparatus. Reversed equilibria were obtained using well-calibrated2.54 cm NaCl furnace assemblies and Ag₈₀Pd₂₀capsules with f_O2bufferedat or near iron-wustite. The equilibrium is located between5.2–5.4, 6.6–6.8, and 8.6–8.8 kb at 880, 940,and 1020?C, respectively, and at 5.2 and 8.8 kb between 865–880and 1020–1030?C, respectively. X-ray refinement data indicate that the hercynite (a = 8.15546?) has approximately 18 per cent inverse character. M?ssbauerspectra reveal that 4 mol per cent of the Fe is ferric (2 percent magnetite component). Broad Mossbauer lines and a Fe²+energy level splitting of 3.7 kJ mol^–1 calculated fromthe Mossbauer spectra are consistent with the X-ray determineddegree of inversion, although no separate octahedral Fe²⁺ spectraldoublet is resolved. Calibration of this equation allows calculation of the equilibrium: Thermobarometers based on the above equilibria are widely applicablein granulite fades rocks and yield pressure/temperature datathat are consistent with other well-calibrated barometers andthermometers.     

Geothermobarometry in Four-phase Lherzolites II. New Thermobarometers, and Practical Assessment of Existing Thermobarometers

On the basis of experiments presented in Part I of this series,most of the published thermobarometers relevant to four-phaseperidotites are tested here for their ability to reproduce experimentalconditions. They were rejected if any systematic discrepancyin either pressure or temperature was discernible. This testcautions against the use of all published versions of thermometersbasad on the compositions of coexisting ortho- and clinopyroxenesand the use of existing barometers based on the Al content oforthopyroxene axxisting with garnet. Therefore, we formulatednew versions of the two-pyroxene thermometer and the Al-in-opxbarometer: with and is in degress Kelvin and P is in kilobars. Our new barometer is of the form (C₁–C₃) and site occupancies are given in the text. Temperatures may also be calculated from the Ca content of opxalone: This thermometer can be applied both to the CMS and the naturalsystem experiments, which may indicate that Fe and Na have counter-balancingeffects on the Ca content of opx. The partitioning of Na between opx and cpx can also serve asa useful thermometer, and was calibrated from natural rock data: where T is in degrees Kelvin, P is in kilobars, and D_Na=Na^opx/Na^cpx. The following three published thermobarometers based on furtherexchange reactions are capable of reprducing experimental conditions:

1. exchangeof Ca between olivine and clinopyroxene as a barometer(P_KB),
2. exchange of Fe and Mg between garnet and clinopyroxene asathermometer (T_Krogh),
3. exchange of Fe and Mg between garnetand olivine as a thermometer(T_O'Neiii).

Our tests also show that the most accurate pressure and temperatureestimates arc obtained from the following combinations of thermometersand barometers:

1. T_BKN+P_BKN,
2. T_BKN+P_KB,
3. T_Krogh+P_BKN,
4. T_O'Ne$$$ll+P_BKN.

     

Geochemical and Isotopic (O, Nd, Pb and Sr) Constraints on A-type Granite Petrogenesis Based on the Topsails Igneous Suite, Newfoundland Appalachians

The voluminous, bimodal, Silurian Topsails igneous suite consistsmainly of ‘A-type’ peralkaline to slightly peraluminous,hypersohnis to subsolvus granites with subordinate syenite,onzonite and diabase, plus consanguineous basalts and highsilicarhyolites. _Nd(T) values from the suite range from –1.5to +5.4; most granitoid components exhibit positive _Nd(T) values(+1.1 to +3.9). Granitoid initial ⁸⁷Sr/⁸⁶Sr and most ¹⁸ O valuesare in the range expected for rocks derived from mantle-likeprotoliths (0.701–0.706 and +6 to +80/). Restricted ²⁰⁷Pb/²⁰⁴Pbvariation is accompanied by significant dispersion of ²⁰⁶Pb/²⁰⁴Pband ²⁰⁸Pb/²⁰⁴Pb. Superficially, petrogenesis by either direct(via fractionation from basalt) or indirect (via melting ofjuvenile crust) derivation from mantle sources appears plausible.Remelting of the granulitic protolith of Ordovician are-typegranitoids can be ruled out, because these rocks exhibit negative_Nd(T) and a large range in ²⁰⁷Pb/²⁰⁴Pb. Geochemical and isotopicrelationships are most compatible with remelting of hybridizedlithospheric mantle generated during arc-continent collision.A genetic link is suggested among collision-related delaminationor slab break-off events and emplacement of ‘post-erogenic’granite suites. A-type granites may recycle previously subductedcontinental material, and help explain the mass balance notedfor modern arcs. However, they need not represent net, new,crustal growth. KEY WORDS: A-type granites; juvenile crust; isotopes; Newfoundland ^*Telephone: (613) 995-4972. Fax: (613) 995-7997. e-mail: jwhalen{at}gsc.emr.ca     

Early-Middle Jurassic Dolerite Dykes from Western Dronning Maud Land (Antarctica): Identifying Mantle Sources in the Karoo Large Igneous Province

A suite of dolerite dykes from the Ahlmannryggen region of westernDronning Maud Land (Antarctica) forms part of the much moreextensive Karoo igneous province of southern Africa. The dykecompositions include both low- and high-Ti magma types, includingpicrites and ferropicrites. New ⁴⁰Ar/³⁹Ar age determinationsfor the Ahlmannryggen intrusions indicate two ages of emplacementat 178 and 190 Ma. Four geochemical groups of dykes have beenidentified in the Ahlmannryggen region based on analyses of60 dykes. The groups are defined on the basis of whole-rockTiO₂ and Zr contents, and reinforced by rare earth element (REE),⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd isotope data. Group 1 were intrudedat 190 Ma and have low TiO₂ and Zr contents and a significantArchaean crustal component, but also evidence of hydrothermalalteration. Group 2 dykes were intruded at 178 Ma; they havelow to moderate TiO₂ and Zr contents and are interpreted tobe the result of mixing of melts derived from an isotopicallydepleted source with small melt fractions of an enriched lithosphericmantle source. Group 3 dyke were intruded at 190 Ma and formthe most distinct magma group; these are largely picritic withsuperficially mid-ocean ridge basalt (MORB)-like chemistry (flatREE patterns, ⁸⁷Sr/⁸⁶Sr_i 0·7035, Nd_i 9). However, theyhave very high TiO₂ (4 wt %) and Zr (500 ppm) contents, whichis not consistent with melting of MORB-source mantle. The Group3 magmas are inferred to be derived by partial melting of astrongly depleted mantle source in the garnet stability field.This group includes several high Mg–Fe dykes (ferropicrites),which are interpreted as high-temperature melts. Some Group3 dykes also show evidence of contamination by continental crust.Group 4 dykes are low-K picrites intruded at 178 Ma; they havevery high TiO₂–Zr contents and are the most enriched magmagroup of the Karoo–Antarctic province, with ocean-islandbasalt (OIB)-like chemistry. Dykes of Group 1 and Group 3 aresub-parallel (ENE–WSW) and both groups were emplaced at190 Ma in response to the same regional stress field, whichhad changed by 178 Ma, when Group 2 and Group 4 dykes were intrudedalong a dominantly NNE–SSW strike. KEY WORDS: flood basalt; depleted mantle; enriched mantle; Ahlmannryggen; Karoo dyke     

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     

Subsolidus Phase Relations in the System MgO--SiO2--Gr--O in Equilibrium with Metallic Cr, and their Significance for the Petrochemistry of Chromium

Subsolidus phase relations have been determined in the systemsSiO₂-Cr-0 and MgO-SiO₂-Cr-O in equilibrium with metallic Cr,at 1100–1500C and 0–288 kbar. There are no ternaryphases in the SiO₂-Cr-O system at these conditions, ie. onlythe assemblage eskolaite + Cr-metal + SiO₂ is found. However,in the MgO-containing system, extensive substitution of Cr²⁺for Mg is observed in (Mg,Cr²⁺)₂SiO₄ olivine, (Mg,Cr²⁺)₂Si₂O₆pyroxene, and (Mg,Cr²⁺)Cr³⁺₂0₄ spinel. Cr ³⁺ levels in olivineand pyroxene are below detection limits. The pyroxene is orthorhombicat monoclinic at higher . The structure of the spinels becomestetragonally distorted at is limited by the breakdown of olivine to pyroxene + spinel+ metal. This maximum amount increases strongly with increasingtemperature, reaching >0.2 at 1500C and 48 kbar. Increasing pressure reduces the maximum. Increasing temperature also increases the maximum amounts of Cr²⁺ which substitute intopyroxene and spinel, indicating that end-member Cr₂Si₂0₆ andCr₃O₄ may become stable above 1650C if melting does not intervene.Powder X-ray diffraction analysis of selected runs has beenused to extract molar volumes of the Mg-Cr²⁺ solid solutionsas a function of composition, which may be extrapolated to predictmolar volumes for Cr₂SiO₄ (olivine), Cr₂Si₂O₆ (ortho- and clino-pyroxene)and Cr₂O₄ (cubic spinel) of 477, 680 and 449 cm³, respectively.The experimental data have been fitted to a thermodynamic model,including free energies of formation for end member Cr₂SiO₄,Cr₂Si₂O₆ and Cr₃O₄. This model is then used to predict the amountsof Cr²⁺ which can be expected in olivine in equilibrium withCr-bearing spinel as a function of T, P and fo₂. This amountincreases strongly with temperature along standard T-fo₂ buffercurves, and is sufficient to explain the observed high Cr contentsof olivine from komatiites and diamond inclusions at reasonableterrestrial fo, values. The lower fo₂ of the lunar environmentresults in significant Cr²⁺ in olivine being stable to muchlower temperatures. The tendency for the oxidation state ofCr, and hence its geochemical properties, to change with temperaturerelative to other redox reactions makes it a potentially usefulmonitor of the temperatures of uppermantle processes, and isa significant factor in the differing styles of igneous differentiationin the Earth and Moon. Corresponding author     

The Solubility of Alumina in Orthopyroxene Coexisting with Garnet in FeO-MgO--Al2O3--SiO2 and CaO--FeO--MgO--Al2O3--SiO2

The pressure-temperature-compositional (P-T-X) dependence ofthe solubility of Al₂O₃ in orthopyroxene coexisting with garnethas been experimentally determined in the P-T range 5–30kilobars and 800–1200 ?C in the system FeO—MgO—Al₂O₃—SiO₂(FMAS). These results have been extended into the CaO—FeO—MgO—Al₂O₃—SiO₂(CFMAS) system in a further set of experiments designed to determinethe effect of the calcium content of garnet on the Al₂O₃ contentsof coexisting orthopyroxene at near-constant Mg/(Mg + Fe). Startingmaterials were mainly glasses of differing Mg/(Mg + Fe) or Ca/(Ca+ Mg + Fe) values, seeded with garnet and orthopyroxene of knowncomposition, but mineral mixes were also used to demonstratereversible equilibrium. Experiments were performed in a piston-cylinderapparatus using a talc/pyrex medium. Measured orthopyroxene and corrected garnet compositions werefitted by multiple and stepwise regression techniques to anequilibrium relation in the FMAS system, yielding best-fit,model-dependent parameters G^o_y= –5436 + 2.45T cal mol^–1,and W^M1_FeA1= –920 cal mol^–1. The volume change ofreaction, V^o, the entropy change, S^o₉₇₀ and the enthalpy changeH^o_1,970, were calculated from the MAS system data of Perkinset al. (1981) and available heat capacity data for the phases.Data from CFMAS experiments were fitted to an expanded equilibriumrelation to give an estimate of the term W^ga_CaMg = 1900 ? 400cal/mole cation, using the other parametric values already obtainedin FMAS. The experimental data allow the development of a arnet-orthopyroxenegeobarometer applicable in FMAS and CFMAS: where This geobarometer is applicable to both pelitic and metabasicgranulites containing garnet orthopyroxene, and to garnet peridoditeand garnet pyroxenite assemblages found as xenoliths in diatremesor in peridotite massifs. It is limited, however, by the necessityof an independent temperature estimate, by errors associatedwith analysis of low Al₂O₃ contents in orthopyroxenes in high-pressureor low-temperature parageneses, and by uncertainties in thecomposition of garnet in equilibrium with orthopyroxene. Ananalysis of errors associated with this formulation of the geobarometersuggests that it is subject to great uncertainty at low pressuresand for Fe-rich compositions. The results of application ofthis geobarometer to natural assemblages are presented in acompanion paper.     

Trace Element and Isotope Geochemistry of the Volcanic Rocks of Bequia, Grenadine Islands, Lesser Antilles Arc: a Study of Subduction Enrichment and Intra-crustal Contamination

Pliocene volcanics on the island of Bequia comprise two interbeddedsuites of basalts and andesites. The isotopically homogeneoussuite (IHS) has a limited range of Sr—Nd—Pb isotopes(⁸⁷Sr/⁸⁶Sr 0.7040–0.7046, ¹⁴³ Nd/¹⁴⁴ Nd 0.5130 and ²⁰⁶Pb/²⁰⁴Pb 19.36–19.51), and mantle-like ¹⁸O values (5.5in clinopyroxene). The isotopically diverse suite (IDS) is characterizedby much wider ranges of radiogenic isotopes (⁸⁷ Sr/⁸⁶Sr 0.7048–0.7077,¹⁴³ Nd/¹⁴⁴ Nd 0.5128–0.5123 and ²⁰⁶ Pb/²⁰⁴ Pb 19.7–20.2),in which all of the Sr and Pb ratios are higher and Nd ratiosare lower than those of the IHS. The IDS is also characterizedby high ¹⁸ O values, up to 7.6 in clinopyroxene. The Sr andPb isotope ratios are too high, and the Nd isotope ratios aretoo low in the IDS for any of these lavas to be derived fromunmodified depleted mantle. Both suites are petrologically very similar and their majorelement compositions and phenocryst contents suggest that theywere formed largely by fractional crystallization of a hydroustholeiitic melt at pressures <3 kbar. The isotopic ratiosand enrichments in large ion lithophile elements (LILE), andto some extent light rare earth elements (LREE), as comparedwith mid-ocean ridge basalts (MORB), of the IHS lavas suggestthat they were derived from a depleted mantle source which hadbeen re-enriched by the addition of 1–4% of a subductioncomponent. This component probably comprised a mixture of dehydrationfluids, and perhaps minor siliceous melts, released from subductingsediments and mafic crust. The extreme isotopic ranges, largeenrichments in incompatible elements, more fractionated LREEpatterns and higher ¹⁸ O values of the IDS lavas are interpretedas resulting from 10–55% assimilation—fractionalcrystallization of sediments, derived from the Guyana Shield,which are present in the arc crust, by IHS type melts. KEY WORDS: trace elements; radiogenic isotopes; arc lavas; Lesser Antilles ^*Corresponding author.     

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.     

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

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

Comparison of 40Ar-39Ar and Rb-Sr Data on Phengites from the UHP Brossasco-Isasca Unit (Dora Maira Massif, Italy): Implications for Dating White Mica

Different lithologies (impure marble, eclogite and graniticorthogneiss) sampled from a restricted area of the coesite-bearingBrossasco–Isasca Unit (Dora Maira Massif) have been investigatedto examine the behaviour of ⁴⁰Ar–³⁹Ar and Rb–Srsystems in phengites developed under ultrahigh-pressure (UHP)metamorphism. Mineralogical and petrological data indicate thatzoned phengites record distinct segments of the P–T path:prograde, peak to early retrograde in the marble, peak to earlyretrograde in the eclogite, and late retrograde in the orthogneiss.Besides major element zoning, ion microprobe analysis of phengitein the marble also reveals a pronounced zoning of trace elements(including Rb and Sr). ⁴⁰Ar–³⁹Ar apparent ages (35–62Ma, marble; 89–170 Ma, eclogite; 35–52 Ma, orthogneiss),determined through Ar laserprobe data on phengites (step-heatingand in situ techniques), show wide intra-sample and inter-samplevariations closely linked to within-sample microchemical variations:apparent ages decrease with decreasing celadonite contents.These data confirm previous reports on excess Ar and, more significantly,highlight that phengite acted as a closed system in the differentlithologies and that chemical exchange, not volume diffusion,was the main factor controlling the rate of Ar transport. Conversely,a Rb–Sr internal isochron from the same eclogite yieldsan age of 36 Ma, overlapping with the time of the UHP metamorphicpeak determined through U–Pb data and thereby corroboratingthe previous conclusion that UHP metamorphism and early retrogressionoccurred in close succession. Different phengite fractions ofthe marble yield calcite–phengite isochron ages of 36to 60 Ma. Although this time interval matches Ar ages from thesame sample, Rb–Sr data from phengite are not entirelyconsistent with the whole dataset. According to trace elementvariations in phengite, only Rb–Sr data from two wet-groundphengite separates, yielding ages of 36 and 41 Ma, are internallyconsistent. The oldest age obtained from a millimetre-sizedgrain fraction enriched in prograde–peak phengites mayrepresent a minimum age estimate for the prograde phengite relics.Results highlight the potential of the in situ ⁴⁰Ar–³⁹Arlaser technique in resolving discrete P–T stages experiencedby eclogite-facies rocks (provided that excess Ar is demonstrablya negligible factor), and confirm the potential of Rb–Srinternal mineral isochrons in providing precise crystallizationages for eclogite-facies mineral assemblages. KEY WORDS: ⁴⁰Ar–³⁹Ar dating; Rb–Sr dating; phengite; SIMS; UHP metamorphism     

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     

Experimental Petrology of Melilite Nephelinites

Experimental study of natural melilite nephelinite lavas ofintermediate K/Na ratio at low pressure (fo₂ reveals the presenceof a peritectic ‘point’ of distributary type (1090?C)for liquids saturated with leucite, nepheline, and spinel. Withdecreasing temperature on the olivine + melilite cotectic, botholivine and melilite react with such liquids to produce high-calciumpyroxene at the peritectic. Both the olivine + high-calciumpyroxene and melilite + high-calcium pyroxene cotectics arestable at temperatures below the peritectic. Olivines coexistingwith such liquids are much more magnesian than those in comparabletholeiitic liquids. The olivine-liquid Fe-Mg distribution coefficient is a monotonically increasing function of silica activity over the composition range spannedby melilite nephelinite, ugandite, alkali basalt, and tholeiitebasalt liquids. The analogous Fe-Mg distribution coefficientfor melilite and liquid is effectively constant , while that for high-calcium pyroxene and liquidis highly dependent on the chemistry of high-calcium pyroxene(cf., Sack & Carmichael, 1984). Pseudoternary liquidus projectionsof multiply saturated liquids coexisting with nepheline, leucite,and spinel (?olivine?high-calcium pyroxene?melilite) have beenprepared to facilitate graphical analysis of the evolution oflava compositions during hypabyssal cooling. Major element chemicalanalyses and petrographic features of lavas from Mt. Nyiragongo,East Africa and Oahu, Hawaii (e.g., Denaeyer et al., 1965; Wilkinson& Stolz, 1983) confirm the validity of these diagrams andthe systematics established from the experimental data. ^*Reprint requests to R.O. Sack