The System CaO-CO2-H2O and the Origin of Carbonatites

The ternary isobaric (TX) prism for the system CaO–CO₂–H₂Owas determined at 1,000 bars pressure between 600? C and 1,320?C. At this pressure, calcite melts incongruently at 1,310? C,portlandite (Ca(OH)₂) melts congruently at 835? C, a binaryeutectic exists between calcite and portlandite at 685? C, meltingbegins at 740? C on the join calcite-water and the univariant(isobaric invariant) equilibria lime?calcite?portlandite?liquidand calcite?portlandite?liquid?vapour occur at 683? C and 675?C, respectively. The latter is the minimum liquidus temperaturein the TX prism, and the composition of this liquid is 65CaO,19CO₂, 16H₂O (in weight per cent). PT curves were determinedfor several univariant equilibria. In the binary system CaO-H₂O,four univariant curves meet at an invariant point, at 810? Cand 100 bars pressure. Portlandite dissociates only at pressuresbelow this point. The minimum liquidus temperature in the ternarysystem varies between 685? C and 640? C in the pressure interval27 bars to 4, 000 bars. Liquids in the system are regarded as simplified carbonatitemagmas in which CaO represents the basic oxides, and CO₂ andH₂O the volatile constituents. The liquids have low viscosityas indicated by the rapid attainment of equilibrium and theobservation that crystal settling takes place in 15-min runs.The existence of such liquids at moderate temperatures througha wide pressure range leaves little reason to doubt a magmaticorigin for those carbonatites which appear to be intrusive.Differentiation could occur in multicomponent magmas by separationof the successive liquid fractions produced by crystallizationof calcite, dolomite, and siderite. The determined phase relationsdo not favour an origin by gas transfer. The results also suggestthat partial melting of limestones is likely at igneous contacts,and that impure limestones may be partially melted during high-graderegional metamorphism.     

Melting of a Hydrous Mantle: III. Phase Relations of Garnet Websterite+H2O at High Pressures and Temperatures

A garnet websterite nodule from the Honolulu volcanic series,Oahu, Hawaii, has been melted in the presence of nearly pureH₂O. The solidus is intermediate between that of peridotiteand gabbro. The curve displays a temperature minimum around20 kb reflecting the breakdown of plagioclase. The Iiquidusis between 1130 ?C and 1150 ?C between 10 and 20 kb vapor pressure.Amphibole (pargasitic hornblende) has an extensive stabilityfield, reaching a maximum temperature about 20 ?C below thegarnet websterite liquidus at 15 kb and a maximum pressure of27.5 kb at 950 ?C. The amphibole-out curve intersects the soliduswith a positive slope. Liquids formed by partial melting of garnet websterite are quartz-normativewithin the stability field of amphibole, but become olivine-normative(tholeiitic) with increasing temperature. Amphibole and clinopyroxeneare enriched in Tschermak's molecule at higher temperatures,pargasite content of amphibole increases with increasing pressure. A garnet websterite-rich upper mantle containing modal olivineyields quartz-normative (13–16 per cent), aluminous (21–4wt. per cent A1₂O₃) melts at 17 P 10 kb and in the presenceof nearly pure H₂O. However, the presence of amphibole controlsthe liquid composition, a situation not found for liquids formedfrom wet peridotite. In contrast to many basalt liquids, liquidof garnet websterite composition cannot fractionate to andesiteby precipitation of amphibole, as amphibole is not a liquidusphase.     

Melting Relations of Basalt with Equilibrium Water Pressure Less Than Total Pressure

Equilibrium H₂O pressure (P_eH2O) was fixed at values less thantotal pressure (P_T) in melting experiments on mixtures of 1921Kilauea tholeiite, H₂O, and CO₂ (58.5 mole per cent H₂O, 41.5mole per cent CO₂), buffered by Ni+NiO. New determinations ofthe beginning of melting of mixtures of 1921 Kilauea tholeiiteand H₂O buffered by quartz+fayalite+magnetite were made at 2and 3 kb. Microprobe analyses of coexisting glass, clinopyroxene,?olivine, ?amphibole were determined for several runs. Decreasing H₂O fugacity (fH₂O) to about six-tenths the fugacityof pure H₂O (f?II₂O) raises the solidus and the upper stabilitylimit of plagioclase. Plagioclase and clinopyroxene coexistin equilibrium with liquid-a feature not observed in the pureH₂O system. Amphibole is stable to about 970 ?C at 2 kb, 1025?C at 5 kb and 1060 ?C at 8 kb. The Al (VI)+Ti contents of theamphibole increase with P, yielding kaersutite at 1050 ?C and8 kb. Calculated modes for the condensed phases reveal large differencesin the amount of glass (liquid) present and large differencesin liquid composition below and above the breakdown temperatureof amphibole at 5 and 8 kb. Liquids coexisting with amphibole,clinopyroxene, olivine, and magnetite are dacitic near the solidusand silica-rich andesites around 1000 ?C at 5 and 8 kb. Theresults of this study substantiate the model for the generationof the calc-alkaline suite by partial melting of H₂O-rich basalts.     

The role of H2O during crystallization of primitive arc magmas under uppermost mantle conditions and genesis of igneous pyroxenites: an experimental study

Exposed, subduction-related magmatic arcs commonly include sections of ultramafic plutonic rocks that are composed of dunite, wehrlite, and pyroxenite. In this experimental study we examined the effects of variable H₂O concentration on the phase proportions and compositions of igneous pyroxenites and related ultramafic plutonic rocks. Igneous crystallization experiments simulated natural, arc magma compositions at 1.2 GPa, corresponding to conditions of the arc lower crust. Increasing H₂O concentration in the liquid changes the crystallization sequence. Low H₂O concentration in the liquid stabilizes plagioclase earlier than garnet and amphibole while derivative liquids remain quartz normative. Higher H₂O contents (>3%) suppress plagioclase and lead to crystallization of amphibole and garnet thereby producing derivative corundum normative andesite liquids. The experiments show that alumina in the liquid correlates positively with Al in pyroxene, as long as no major aluminous phase crystallizes. Extrapolation of this correlation to natural pyroxenites in the Talkeetna and Kohistan arc sections indicates that clinopyroxenes with low Ca-Tschermaks component represent near-liquidus phases of primitive, Si-rich hydrous magmas. Density calculations on the residual solid assemblages indicate that ultramafic plutonic rocks are always denser than upper mantle rocks in the order of 0.05 to 0.20 g/cm³. The combination of high pressure and high H₂O concentration in the liquid suppresses plagioclase crystallization, so that ultramafic plutonic rocks form over a significant proportion of the crystallization interval (up to 50% crystallization of ultramafic rocks from initial, mantle-derived liquids). This suggests that in subduction-related magmatic arcs the seismic Moho might be shallower than the petrologic crust/mantle transition. It is therefore possible that calculations based on seismic data have overestimated the normative plagioclase content (e.g., SiO₂, Al₂O₃) of igneous crust in arcs.     

Melting Behavior of Simplified Lherzolite in the System CaO-MgO-Al2O3-SiO2-Na2O from 7 to 35 kbar

Phase equilibrium data have been collected for isobaricallyunivariant melting of simplified Iherzolite compositions inthe system CaO-MgO-Al₂O₃ SiO₂-Na₂O over a pressure range of7–35 kbar. These data permit the melting behavior of awide variety of model lherzolite compositions to be determinedquantitatively by algebraic methods. Two P-T univariant meltingreactions, corresponding to plagioclase to spinel lherzoliteand spinel to garnet lherzolite, are identified as peritectic-typetransitions and have positive Clapeyron slopes. The univariantcurves move to higher pressures and temperatures with increasingNa₂O in the liquid. The effect of the univariant curves on meltingis to produce low-temperature regions and isobarically invariantmelting intervals along lherzolite solidi. In the plagioclaselherzolite stability field, melting of four-phase model lherzoliteis pseudo-invariant, occurring over small temperature intervals(5C) and producing liquids that are quartz tholeiites at <8kbar and olivine tholeiites at >8 kbar. Calculated equilibriumconstants for plagioclase-liquid equilibria show both temperatureand pressure dependence. Plagioclase with anorthite content(AN) >90 mol%, as observed in some oceanic basalts, can crystallizefrom liquids with <1% Na₂O. Melting of spinel lherzoliteis not pseudo-invariant but occurs over large temperature intervals(15–60 C), producing a wide range in liquid compositions,from alkali basalts and alkali picrites at low to moderate degreesof melting (<1–10%) to olivine tholeiites and picritesat higher degrees of melting (>10%). On the basis of limiteddata in the garnet Iherzolite field, melts from garnet lherzoliteare more silica rich for a given degree of melting than meltsfrom spinel lherzolite, and liquid compositions trend towardenstatite with increase in pressure. Source fertility (especiallyNa₂O content) has a strong control on the temperature of meltingand liquid composition. Less fertile sources produce smalleramounts of liquids richer in normative silica. For certain bulkcompositions (high SiO₂ and low Al₂O₃), spinel is not a stablephase along the lherzolite solidus.     

Melting of a Hydrous Mantle: II. Geochemistry of Crystals and Liquids Formed by Anatexis of Mantle Peridotite at High Pressures and High Temperatures as a Function of Controlled Activities of Water, Hydrogen, and Carbon Dioxide

The system peridotite-H₂O–CO₂ serves as a simplified modelfor the phase relations of mantle peridotite involving morethan one volatile component. Run products obtained in a studyof phase relations of four mantle peridotites in the presenceof H₂O- and (H₂O+CO₂)- bearing vapors and with controlled hydrogenfugacity (f_H2) at high pressures and temperatures have beensubjected to a detailed chemical investigation, principallyby the electron microprobe. Mg/(Mg+Fe) of all phases generally increases with increasingtemperature and with increasing Mg/(Mg+Fe) of the starting material.This ratio appears to decrease with increasing pressure forolivine, and for amphibole coexisting with garnet. Decreasingf_H2 from that of IW buffer to that of MH buffer decreases Mg/(Mg+Fe)of the partial melt from approximately 0-85 to approximately0.50, whereas the Fo content of coexisting olivine increasesslightly less than 3 per cent and the Mg/(Mg+Fe) of clinopyroxeneincreases about 4 per cent. However, the variations in Fo contentof olivines are within those observed in olivines from naturalmantle peridotite. The chemistry of other silicate mineralsdoes not significantly reflect variations of f_H2. Consequently,the peridotite mineralogy and/or chemistry is not a good indicatorfor the f_H2 conditions during crystallization. All crystalline phases, except amphibole, and to some extentgarnet, show increasing Cr content with increasing temperatureand increasing Cr content of the starting material, resultingin a positive correlation with Mg/(Mg+Fe). Partial melts aredepleted in Cr₂O₃ relative to the crystalline phases. High Mg/Mg+Fe)and Cr₂O₃ are thus expected in crystal residues after partialmelting. The absolute values depend on degree of melting andthe composition of the parent peridotite. Liquids formed by anatexis of mantle peridotite are andesiticunder conditions of X_H2O^v > 0.6 to at least 25 kb total pressureand to more than 200?C above the peridotite solidus. This observationsupports numerous suggestions that andesite genesis in islandarcs may result from partial melting of underlying peridotitemantle. In contrast to basaltic rocks, the absence of amphibole(paragasitic hornblende) does not affect the silica-saturatednature of the liquids. Increasing K₂O content of the startingmaterial (up to 1 wt. per cent K₂O) results in increasing potassiumcontent of the amphibole (1 wt. per cent K₂O) as well as theappearance of phlogopite. The liquid under these conditionsis relatively K₂0-poor (less than 1 wt. per cent K₂O). Partial melts are olivine normative with X_H2O 0.5, and initialliquids contain normative ol and ne at X_H2O 0.4. The alkalinityof these liquids increases with decreasing X_H2O below valuesof 0.5. The (ol+opx)-normative liquids resemble oceanic basaltswhereas (ol+ne)-normative liquids resemble olivine nepheliniteand melilite basalt. Low aHlo and high a_Co2 conditions may bethose under which kimberlites and related rocks are formed inthe mantle.     

The System MgSiO3--CaMgSi2O6

Subsolidus and liquidus phase relations along the join MgSiO₃—CaMgSi₂O₆have been determined from the results of dry and hydrothermalruns. Two-pyroxene mixtures which crystallize within the solvusin dry runs form cryptoperthites, and X-ray methods must beused to determine their compositions and locate the boundariesof the solvus. Mg-rich and Ca-rich pyroxenes can, however, bedistinguished in well-crystallized hydrothermal runs by opticaltechniques. The results obtained indicate that solid solution along thisjoin is more restricted than was found by Atlas (1952). Thesolvus intersects the solidus over a composition interval of42 wt per cent. Additional data on the rhombic enstatite protoenstatiteinversion are consistent with Atlas's value of 985??10?C. Thisinversion has proved to be very sensitive to pressure, and thedT/dP slope of the transition is 84??10?/kb. The crystallization of natural pyroxenes from basaltic magmasis reviewed in the light of the experimental data. The solidsolution shown by Fe-poor pyroxene pairs from layered intrusionssuch as the Skaergaard is remarkably restricted. The temperatureof crystallization of these pyroxenes as deduced from the solvuson the join MgSiO₃—CaMgSi₂O₆ is about 1000? C. In makingthis estimate it is assumed that any subsolidus exsolution hasnot proceeded beyond the stage of lamellae formation. This temperatureis below the dry solidus of basalt, and the result indicatesthat either the solid solution shown by these natural pyroxenesis influenced by impurities such as Al or Fe', or the meltinginterval of the magmas which formed the intrusions was loweredby a substantial vapor pressure of H₂O. It is suggested that pyroxenes which have crystallized fromextrusive basalts and which have compositions that plot in thecentral portion of the pyroxene quadrilateral are metastablesolid solutions formed by quick cooling. Available informationis not sufficient to clarify the relationship between pigeoniteand the various polymorphs of MgSiO₃. It is probable, however,that there is a first-order inversion between pigeonite andprotoenstatite, and possible phase relations between these formsin the system MgSiO₃—FeSiO₃ are discussed.     

Petrology of some Glaucophane Schists and Related Rocks from Taiwan

Detailed laboratory study has been made on pre-Tertiary coarse-grainedglaucophane schist, garnet-epidote amphibolite, and epidoteamphibolite in the eastern slope of the Central Mountain Range,Taiwan. These petrotectonic assemblages are considered to beexotic tectonic blocks emplaced within the feebly metamorphosedin situ graphite and quartzose schists of the Yuli belt. Thinlenses of Mn-rich metamorphosed tuff are intercalated withinthe metabasaltic rocks. Such high MnO (2 wt. per cent) and lowMgO (3–4 wt. per cent) tuffaceous rocks are similar inbulk composition to some volcanic clays collected in deep oceanbasins. They consist of the characteristic assemblage Mn-bearinggarnet (5–7 wt. per cent MnO and 30 volume per cent inthe rock)+muscovite+epidote+hornblende+quartz+ albite+rutile?pyrite. Successive stages of conversion of garnet-epidote amphiboliteto blueschist assemblages were noticed. The most recrystallizedschists display abundant Mn-bearing garnet, zoned amphibole,phengite, zoned epidote, stilpnomelane, chlorite, quartz, minoralbite, magnetite, and sphene. The recrystallization processis nearly isochemical except the glaucophane schists appearto be more oxidized and contain more Na₂O than the relict amphibolites.Intimately associated amphibolites of basaltic composition,in contrast, contain the assemblage hornblende+paragonite+epidote+chlorite+quartz+albite+rutile. Microprobe analyses of the coexisting minerals in glaucophaneschists, garnet-epidote amphibolites and epidote amphibolitesyield the following results: (1) garnets, consisting of almandine,spessartine, and grossular components, are less Mn and Mg-richcompared to those in in situ metabasalts of the Franciscan;(2) rim epidotes of the glaucophane schists are more pistastic(X_Fe=0?27–0?30) than that of the garnet-epidote amphibolite(0?2–0?22) implying higher fO₂ values for the glaucophanization;(3) phengitic micas of the glaucophane schist have less Al₂O₃content (29 wt. per cent) than those of the garnet-epidote amphibolite(32 wt. per cent) whereas micas of epidote amphibolites areparagonites with K/(K+Na) ratio of 0?04; (4) the zoned amphibolesshow glaucophane occurring marginal to cores of calcic amphibole.Sodic amphiboles with Al₂O₃ of 6-? to 10?4 wt. per cent arecrossite-glaucophane whereas all calcic amphiboles analyzedare barroisite-pargasite (Al₂O₃ greater than 10 wt. per cent). The garnet-epidote-rutile bearing glaucophane schist of Taiwanprobably recrystallized at temperatures above 350 ?C (the epidotezone) whereas the lawsonite-sphene glaucophane schists of theFranciscan equilibrated below 350 ?C (the lawsonite zone). TheMn-rich basaltic tuffs and their associated flows appear tohave been metamorphosed at profound depths and at the relativelyhigh temperatures of the epidote amphibolite facies, succeededlater by glaucophane schist facies metamorphism at lower temperatures.     

Compositions and Structural States of Anhydrous Mg-Cordierites: A Re-investigation of the Central Part of the System MgO-Al2O3-SiO2

The central portion of the system MgO–Al₂O₃–SiO₂has been studied with the aim of determining the range of solidsolution, as well as the stability limits of the various structuralstates of the ternary compound cordierite. The previously suggestedlimited solid solution between cordierite of the composition2MgO? 2Al₂O₃? 5SiO₂ (2: 2: 5) and SiO₂ is now believed to existonly metastably. Between 800? and 1,300? C the composition ofcordierite was found to be invariably 2MgO. 2Al₂O₃ 5SiO2. Above1,300?C, however, there is evidence for the existence of limitedsolid solution in cordierite (2: 2: 5) toward a theoreticalcompound ‘Mg-beryl’ (3: 1: 6). The existence ofcordierite solid solution at liquidus temperatures has an importantbearing on the melting relations of many compositions withinthe system. Because of this solid solution the courses of crystallizationof melts consisting of normative cordierite (2: 2: 5) and smallamounts of MgSiO3, for example, have to follow parts of theboundary curve between the cordierite and spinel fields withthese two phases coprecipitating over a limited range of temperatures.The dividing line between compositions which complete theircrystallization at the ternary eutectic forsterite+protoenstatite+cordierite+liquid,1,364? ?3? C, and those which complete their crystallizationat the ternary eutectic protoenstatite +cordierite+tridymite+liquid,1, 355??3? C was formerly considered to be the join MgSiO3-cordierite(2: 2: 5). Because of solid solution in cordierite coexistingwith liquid this dividing line is displaced slightly in thedirection toward more siliceous bulk compositions. Furthermore,the temperature maximum along the boundary curve cordierite+protoenstatite+liquid cannot lie at the intersection of this boundary curvewith the join MgSiO3–2: 2: 5, but with the tie line MgSiO3-cordieritess.The position of this temperature maximum thus moves closer tothe ternary eutectic protoenstatite+cordierite+tridymite+liquid.Temperatures and compositions of some of the invariant pointsin the system have been redeter-mined.     

Petrology of the Ejected Plutonic Blocks of the Soufriere Volcano, St. Vincent, West Indies

The ejected blocks of the Soufrière volcano consist ofthe mineral phases anorthite (An₉₆-An₈₉; average An₉₃), olivine(Fo₇₉-Fo₆₇; most frequent interval Fo_74-71), salite con taining5–6 per cent Al₂, O₃, hastingsitic amphibole, and magnetitecontaining 6 per cent A1₂O₃, 4 per cent MgO, 7 per cent TiO₂.The minerals occur in various proportions and textures. Theyare virtually unzoned and represent material which has beenejected at, and quenched from, a high temperature. The interstitialscoria present among the mineral grains in the blocks has thecomposition of a saturated sub-alkaline aluminous basalt, andis believed to represent the liquid phase with which the mineralswere in equilibrium at depth. The high-temperature mineralogy,the textures and structures of the rocks support the view thatthe blocks represent crystal cumulates which have crystallizedunder high water-vapor pressures from a fractionating basaltmagma at a depth approximating 6 km. The bulk composition ofthe blocks is such that the resultant liquid fractions are enrichedin silica. Fractional crystallization may be an important factorin the evolution of some calc-alkaline suites.     

Distribution of the Period Four Transition Elements among Olivine, Calcic Clinopyroxene and Mafic Silicate Liquid: Experimental Results

The distribution of Ti⁴⁺, V³⁺, Cr³⁺, Mn²⁺, Fe(total), Co²⁺ andNi²⁺ among synthetic olivine, calcic clinopyroxene and maficsilicate liquid has been studied between 1125 and 1250 ?C underanhydrous conditions at 1 bar total pressure. The distributionof iron and magnesium among the three phases was concluded tobe independent of temperature and may be described by the twoequations Titanium and vanadiumdid not enter olivine in significant amounts. The mean valueof the ratio (wt. per cent TiO₂ in Cpx)/(wt. per cent TiO₂ inL) was 0.29?0.04 for assemblages in which the liquid had botholivine and hypersthene in the norm but the ratio was greaterif the liquid was nepheline normative. Vanadium was concentratedin the pyroxene in some experiments and in the liquid in others,but it was not possible to conclude whether the change in distributionbehavior was due to varying temperature or changing liquid composition.Equilibrium partitioning of chromium was not achieved but theresults indicate that Cr₂O₃ was most strongly enriched in clinopyroxeneand showed a slight preference for olivine over the liquid.The divalent transition elements were each enriched in olivinerelative to clinopyroxene and the degree of enrichment increasedin the order predicted by crystal field theory. The mean (wt.per cent oxide in 01)/(wt. per cent oxide in Cpx) ratios were2.0 for MnO, 2.4 for FeO, 3.9 for CoO and 5.6 for NiO. Manganesewas enriched in olivine relative to the liquid and in the liquidrelative to the clinopyroxene. Cobalt and nickel were more concentratedin the crystalline phases than in the liquid but the degreeof enrichment was markedly less in the experiments in whichthe liquids were more mafic.     

The System MgO-CO2-H2O at High Pressures and Temperatures

The system MgO-CO₂-H₂O has been studied up to 1,400? C and 4,000bars pressure using the sealed-capsule quenching technique.No melting was observed. At 1,000 bars pressure magnesite dissociatesat 780? C, and brucite at 635? C, to periclase and vapor. Theunivariant reaction MgCO₃?Mg(OH)₂ MgO + V proceeds at 630?C, at 1,000 bars and at 700? C, at 4,000 bars. Solubility measurementsshow that, at 1,000 bars and temperatures up to 1,000? C, lessthan 1.5 weight per cent MgO is dissolved in the vapor phase.Brucite is unstable in the presence of vapors containing morethan a small amount of CO₂. The maximum percentage of CO₂ ina vapor that can coexist with brucite increases with decreasingpressure and with increasing temperature: 6 weight per centCO₂ is the maximum at 630? C, 1,000 bars, and 4 weight per centat 700? C, 4,000 bars. The phase relations in the isobaric TXprism for 1,000 bars pressure are described. The results illustratetwo dissociation reactions, decarbonation and dehydration, occurringin the presence of a vapor phase containing two volatile components,H₂O and CO₂. Applications to metamorphism are briefly discussed.     

Coexisting Amphiboles

Chemical analyses for the following amphibole pairs are presented:anthophyllite—tremolite (or actinolite, or hornblende),cummingtonite (or grunerite)–actinolite (or hornblende),cummingtonite (or grunerite)–anthophyllite (or gedrite),and manganoan cummingtonitemagnesioriebeckite. Nineteen analyses of such pairs are quoted from the literature,and thirty-seven additional pairs have been newly analyzed byelectron probe techniques. Quantitative microprobe determinationsof Si, Al, Fe, Mn, Mg, Ca, and Na were made on polished thin-sections,using naturally occurring, analyzed, homogeneous amphibolesas standards. The literature analyses and the electron probeanalyses for metamorphic, two-amphibole assemblages are givenfor amphiboles in physical contact, which show no textural evidenceof one amphibole being a reaction or alteration product of theother. The chemical data for some of the volcanic, two—amphiboleassemblages were obtained from occurrences that probably donot represent equilibrium pairs. The chemical data are used to determine the extent of the miscibilitygaps between the various amphibole series and the fractionationof the major elements between the two amphiboles of a pair.Anthophyllite and members of the cummingtonite-grunerite seriesgenerally have a larger Fe(total)/Mg ratio than the coexistingcalcic amphibole. The maximum CaO, Al₂O₃and Na₂O contents ofcummingtonite in metamorphic cummingtonite—hornblendepairs are 19 and 32, 02 weight per cent, respectively. Themaximum CaO, A1₂O₃, and Na₂O contents of cummingtonite in metamorphiccummingtonite-hornblende pairs are 19, 32, and 02 weightper cent, respectively. Larger CaO and Al₂O₃ values reportedin the literature were found to be too high because of admixtureof actinolite or hornblende in the analyzed separates. Smallamounts of MnO tend to concentrate preferentially in anthophylliteor cummingtonite of anthophyllite-hornblende and cummingtonite-hornblendepairs. Anthophyllite-cummingtonite pairs may show very similarFe(total)/Mg ratios and differ slightly in Al₂O₃ content only.     

Equilibrium Compositions of Coexisting Garnet and Orthopyroxene: Experimental Determinations in the System FeO-MgO-Al2O3-SiO2, and Applications

We have determined the Fe-Mg fractionation between coexistinggarnet and orthopyroxene at 20–45 kb, 975–1400?C,and the effect of iron on alumina solubility in orthopyroxeneat 25 kb, 1200?C, and 20 kb, 975?C in the FMAS system. The equilibriumcompositions were constrained by experiments with crystallinestarting mixtures of garnet and orthopyroxene of known initialcompositions in graphite capsules. All iron was assumed to beFe²⁺. A mixture of PbO with about 55 mol per cent PbF₂ provedvery effective as a flux. The experimental results do not suggest any significant dependenceof K_D on Fe/Mg ratio at T 1000?C. The lnK_D vs. l/T data havebeen treated in terms of both linear and non-linear thermodynamicfunctional forms, and combined with the garnet mixing modelof Ganguly & Saxena (1984) to develop geothermometric expressionsrelating temperature to K_D and Ca and Mn concentrations in garnet. The effect of Fe is similar to that of Ca and Cr³⁺ in reducingthe alumina solubility in orthopyroxene in equilibrium withgarnet relative to that in the MAS system. Thus, the directapplication of the alumina solubility data in the MAS systemto natural assemblages could lead to significant overestimationof pressure, probably by about 5 kb for the relatively commongarnetlherzolites with about 25 mol per cent Ca+Fe²⁺ in garnetand about 1 wt. per cent Al₂O₃ in orthopyroxene.     

The System Na2O-Al2O3-Fc2O3-SiO2 at 1 Atmosphere, and the Petrogenesis of Alkaline Rocks

Equilibria involving acmite, albite, nepheline, quartz, anda liquid phase constitute the petrologically important partof the system Na₂O–Al₂O₃–Fe₂O₂–SiO₂, and theunivariant and invariant relations provide useful analogiesfor a wide variety of alkaline igneous rocks. These relationsare dominated by the incongruent melting behaviour of acmite,which does not appear on the liquidus of the join acmite-nepheline-silica;instead, a broad field of hematite is present and acmite crystallizesonly from liquids containing potential sodium silicate. Consequently,the oversaturated and undersaturated eutectics, correspondingto granitic and nepheline syenitic liquids, are rich in sodiumsilicate and distinct from those found in Petrogeny's Residuasystem: the temperatures of the eutectics are 7285C and 7155C, respectively. Survival of peralkaline granite in the aluminouscontinental crust can be explained by the strongly peralkalinecomposition of the oversaturated eutectic. Magma of this typemay be the primitive granite of the non-orogenic zones. Theubiquitous alkali metasomatism around alkaline complexes canalso be interpreted in terms of residual liquids enriched inalkali silicates. Transition from undersaturated to oversaturatedliquids is possible by fractionation of hematite and a new processfor achieving the reverse transition has been found. This dependson the substitution of Fe³ for Al³ in feldspar and suggestsa more important role for syenite in any scheme of petrogenesis. Each of the two eutectics is linked to a corresponding peritecticat which hematite reacts to give acmite. The liquid at the undersaturated,quaternary reaction point is of ijolitic type, providing thefirst intimation that ijolite may represent a low-melting fractionin nature. The system Na₂O–Al₂O₃–Fe₂O₃–SiO₂thus constitutes the peralkaline residua system and on thisbasis a coherent picture of stable continental magmatism canbe constructed. Ijolite is seen as the low-melting fractionfrom a range of peralkaline compositions and from rocks suchas melilite basalt, while the frequently associated carbonatiteis considered to be the volatile-rich, fugitive material fromthe mantle. Such a relationship is consistent with the dualassociation of carbonatite with either ijolite or kimberliteunder different tectonic conditions. The more common syenite,nepheline syenite, and alkaline granite of the non-orogenicregions are regarded as low-melting fractions from basalticmaterials in the deep crust. Most of this activity, involvingmagmas of residual type, could thus be explained in terms ofpartial melting in the deep crust and upper mantle. A possiblemechanism for this would be arching of the rigid continentalcrust, the consequent relief of lithostatic load giving riseto melting, and the concentration of fugitive constituents,in the underlying zones.     

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.     

Upper Mantle Amphiboles and Micas and TiO2, K2O, and P2O5 Abundances and 100 Mg/(Mg+Fe2+ Ratios of Common Basalts and Andesites: Implications for Modal Mantle Metasomatism and Undepleted Mantle Compositions

Modal mantle metasomatism, involving the re-enrichment of depletedmantle by the introduction or production of new hydrous phases,apatite and other minerals, has been proposed as a criticalprecursor to alkaline volcanism. The merits of the modal metasomatismmodel are evaluated by examining whole-rock 100 Mg/(Mg+Fe²⁺)ratios and the abundances of TiO₂, K₂O and P₂O₅ in mafic volcanicsspanning the mafic alkaline-subalkaline compositional spectrum.Upper mantle amphiboles and micas are also discussed becausethey would be major donors of Ti, Fe, and K to melts duringanatexis of either modally metasomatized depleted mantle orundepleted mantle. Compared with tholeiitic and calc-alkaline basalts and andesites,basanites and alkali basalts and alkali andesites are neitherdistinctive nor unique by virtue of persistant or well-definedhigher abundances of TiO₂, K₂O, and P₂O₅ or lower 100 Mg/(Mg+Fe₂₊)ratios, features which might reflect precursor modal metasomatismof the alkaline sources. Some basanites and alkali basalts dohave higher abundances of TiO₂, K₂O, and P₂O₅ than some tholeiitesbut these abundances may be the result of lower degrees of meltingof similar undepleted mantle sources for both magma types. The most widespread mantle phases of inferred metasomatic originare interstitial amphiboles and micas in Group I spinel peridotitexenoliths. These have high 100 Mg/(Mg+Fe) ratios ({small tilde}90) and high Cr₂O₃ and low TiO₂ abundances, and the K₂O/Na₂Oratios of the amphiboles (chromian pargasites) are low, generallyless than 0?3. Interstitial amphiboles and micas developed asa result of near-isochemical hydration reactions which largelyinvolved Cr-spinel and Cr-diopside. Their formation was probablyinduced in many instances by fluids derived from crystallizingmafic magmas. Metasomatized Group I xenoliths with interstitialhydrous phases remain depleted in TiO₂, K₂O, and P₂O₅, and theyretain the high 100 Mg/(Mg+Fe) ratios characterizing depletedGroup I xenoliths. Together with the low K₂O/Na₂O ratios, thesefeatures preclude such peridotites as suitable sources of mostalkaline (and subalkaline) volcanics. It is suggested that modalmetasomatism plays an insignificant role in the genesis of mostmantle-derived mafic volcanics. Compared with the interstitial phases, kaersutitic amphibolesand titaniferous micas from vein, Group II inclusion and megacrystupper mantle parageneses have lower 100 Mg/(Mg+Fe) ratios andCr₂O₃ contents, and much higher TiO₂ abundances. K₂O/Na₂O ratiosof the Ti-amphiboles are also much more wide-ranging (0?3 togreater than 1?0). These Fe, Ti-rich amphiboles and micas areneither widespread nor pervasive phases in metasomatized mantle.They are directly related to alkaline magmatism in the uppermantle where they may be associated with incompatible elementenrichment of peridotite wallrocks in the immediate vicinityof frozen conduits of alkaline mafic magmas. The varying K₂O/Na₂O ratios of mafic volcanics (MORB constitutea major exception) indicate that the principal K-bearing phasesin undepleted mantle are kaersutitic amphibole and titaniferousmica, in varying proportions. The former is probably the majorsource of Ti and K for low K/Na volcanics (K₂O/Na₂O < 0?5)and also many medium K/Na types (0?5 < K₂O/Na₂O < 1?0),whereas mica is more likely to be the major K-bearing phasein the source regions of high K/Na extrusives (K₂O/Na₂ >1?0). Experimental data indicate that kaersutitic amphibole,mica and apatite probably coexist in undepleted spinel- andgarnet lherzolites at pressures up to 25 kb, with mica persistingto pressures as high as 50 kb. It is proposed that undepleted asthenospheric mantle is heterogeneouswith respect to its amphibole, mica, and apatite contents (andhence TiO₂, K₂O, and P₂O₅ abundances and K₂O/Na₂O ratios), andalso with respect to 100 Mg/(Mg+Fe²⁺ ) ratios which may be significantlyless than the ratios generally assigned to undepleted mantle,namely 88–90.     

Water-Saturated and -Undersaturated Melting of Metaluminous and Peraluminous Crustal Compositions at 10 kb: Evidence for the Origin of Silicic Magmas in the Taupo Volcanic Zone, New Zealand, and Other Occurrences

The melting relations of two proposed crustal source compositionsfor rhyolitic magmas of the Taupo Volcanic Zone (TVZ), New Zealand,have been studied in a piston-cylinder apparatus at 10 kb totalpressure and a range of water activities generated by H₂O-CO₂vapour. Starting materials were glasses of intermediate composition(65 wt.% Si0₂ representing a metaluminous ‘I-type’dacite and a peraluminous ‘S-type’ greywacke. Crystallizationexperiments were carried out over the temperature range 675to 975?C, with aH₂O values of approximately 1?0, 0?75, 0?5,and 0?25. Talc-pyrex furnace assemblies imposed oxygen fugacitiesclose to quartz-fayalite-magnetite buffer conditions. Assemblages in both compositions remain saturated with quartzand plagioclase through 675–700?C at high aH₂O, 725–750?Cat aH₂O0?5, and 800–875?C at aH₂O0?25, corresponding to<60–70% melting. Concentrations of refractory mineralcomponents (Fe, Mg, Mn, P, Ti) in liquids increase throughoutthis melting interval with increasing temperature and decreasingaH₂O. Biotite and hornblende are the only mafic phases presentnear the solidus in the dacite, compared with biotite, garnet,gedritic orthoamphibole, and tschermakitic clinoamphibole inthe greywacke. Near-solidus melting reactions are of the type:biotite + quartz + plagioclase = amphibole ? garnet, potentiallyreleasing H₂O for dehydration melting in the greywacke, butproducing larger amounts of hornblende and releasing littleH₂O in the dacite. At aH₂O0?25 and temperatures 825–850?C,amphibole dehydration produces anhydrous mineral phases typicalof granulite fades assemblages (clinopyroxene, orthopyroxene,plagioclase?quartz in the dacite; garnet, orthopyroxene, plagioclase?quartzin the greywacke) coexisting with melt proportions as low as40%. Hornblendce-saturated liquids in the dacite are weaklyperaluminous (0?3–1?6 wt.% normative C—within therange of peraluminous TVZ rhyolites), whereas, at aH₂O0?25 andtemperatures 925?C, metaluminous partial melt compositions (upto 1?8 wt.% normative Di) coexist with plagioclase, orthopyroxene,and clinopyroxene. At all water activities, partial melts ofthe greywacke are uniformly more peraluminous (1?5–2?6wt.% normative C), reflecting their saturation in the componentsof more aluminous mafic minerals, particularly garnet and Al-richorthopyroxene. A metaluminous source for the predominantly Di-normativeTVZ rhyolites is therefore indicated. With decreasing aH₂O the stability fields of plagioclase andquartz expand, whereas that of biotite contracts. These changesare reflected in the proportions of normative salic componentsin partial melts of both the dacite and greywacke. At high aH₂O,partial melts are rich in An and Ab and poor in Or (trondhjemitic-tonalitic);with decreasing aH₂O they become notably poorer in An and richerin Or (granodioritic-granitic). These systematic variationsin salic components observed in experimental metaluminous tostrongly peraluminous melts demonstrate that a wide varietyof granitoid magmas may be produced from similar source rocksdepending upon P-T-aH₂O conditions attending partial melting.Some peraluminous granitoids, notably trondhjemitic leucosomesin migmatites, and sodic granodiorites and granites emplacedat deep crustal levels, have bulk compositions similar to nearsolidus melt compositions in both the dacite and greywacke,indicating possible derivation by anatexis without the involvementof a significant restite component.     

Subsolidus and Partial Melting Reactions in the Quartz-excess CaO+MgO+Al2O3+SiO2+H2O System under Water-excess and Water-deficient Conditions to 10 kb: Some Implications for the Origin of Peraluminous Melts from Mafic Rocks

Experimental results up to 10 kb pressure are presented on thestability of amphibole in the quartz-excess CaO+MgO+Al₂O₃ (CMASH)system under H₂O)-excess and H₂O deficient conditions. Amphiboleis stable above the solidus under H₂O-excess conditions whereasunder H₂O-deficient conditions dehydration melting of amphibole-bearingassemblages defines the solidus. The successive appearance ofamphibole, talc, and zoisite with increasing pressure considerablymodifies the plagioclase-pyroxene-garnet-kyanite reactions documentedexperimentally in the CaO+MgO+Al₂O₃+SiO₂ system for gabbro-granulite-eclogitetransitions. Although both clino pyroxene and cordierite (withanorthite+orthopyroxene+quartz) may melt eutectically at oneatmosphere to form diopside-normative and corundum-normativemelts respectively, at higher pressures under H₂O-excess conditionsthe peritectic melting of mafic rock compositions produces corundum-normativeliquids together with either clinopyroxene or amphibole. Dehydrationmelting produces melts which are not corundum-normative. Thesedata are used to discuss the origins and evolution of contrastingbasalt-andesite-dacite-rhyolite volcanic suites and graniticplutons, many of whose silicic variants are corundum-normativein character, such as the Toba luff ignimbrites, Indonesia (Beddoc-Stephenset al., 1983) and I-type granite minimum melts (White &Chappell, 1977). In contrast, it is proposed that for the Cascadesbasalt-andesite-dacite-rhyolite suite the ortho pyroxene-plagioclase-quartzthermal divide was maintained up to rhyolite compositions, therebyprohibiting the derivation of corundum-normative rocks fromdiopside-normative parent magmas. The deduced reaction relations between pyroxenes, amphibole,plagioclase, quartz, and liquid are used to explain the absenceor extreme scarcity of hydrous phases in some hydrous magmas.These phase relations can also explain the development of laterplagioclase overgrowths on resorbed plagioclase cores in graniticintrusives, and the general absence of resorption and overgrowthsin chemically equivalent extrusive rocks. A theoretical analysis of the partial melting of forsterite-bearingassemblages in the CaO+MgO+Al₂O₃+SiO₂+H₂O system shows thatunder H₂O-excess conditions partial melting may generate corundum-normative(but low SiO₂) melts from a peridotite source at shallow depths.     

Petrology of the Blue Mountain Complex, Marlborough, New Zealand

Blue Mountain is a central-type alkali ultrabasic-gabbro ringcomplex (1?1?5 km) introducing Upper Jurassic sediments, Marlborough,New Zealand. The ultrabasic-gabbroic rocks contain lenses ofkaersutite pegmatite and sodic syenite pegmatite and are intrudedby ring dykes of titanaugite-ilmenite gabbro and lamprophyre.The margin of the intrusion is defined by a ring dyke of alkaligabbro. The plutonic rocks are cut by a swarm of hornblende-biotite-richlamprophyre dykes. Thermal metamorphism has converted the sedimentsto a hornfels ranging in grade from the albite-epidote hornfelsfacies to the upper limit of the hornblende hornfels facies. The rocks are nepheline normative and consist of olivine (Fo_82-74),endiopside (Ca₄₅Mg₄₈Fe₇-Ca₃₆Mg₅₅Fe₉), titanaugite (Ca₄₀Mg₅₀Fe₁₀-Ca₄₄Mg₃₉Fe₁₇),plagioclase (An_73-18), and ilmenitetitaniferous magnetite, withvarious amounts of titaniferous hornblende and titanbiotite.There is a complete gradation between end-iopside and titanaugitewith the coupled substitution R_y^+z+Si(Ti⁺⁴+Fe⁺³)+Al⁺³ and asympathetic increase in CaAl₂SiO₆ (0?2-10?2 percent) and CaTiAl₂O₆(2?1-8?1 per cent) with fractionation. Endiopside shows a small,progressive Mg enrichment along a trend subparallel to the CaMgSi₂O₆-Mg₂Si₂O₆boundary, and titanaugite is enriched in Ca and Fe⁺²+Fe⁺³ withdifferentiation. Oscillatory zoning between endiopside and titanaugiteis common. Exsolved ilmenite needles occur in the most Fe-richtitanaugites. The amphiboles show the trend: titaniferous hornblende(1?0–5?7 per cent TiO₂)kaersutite (6?4 per cent TiO₂)Fe-richhastingsite (18?0–19?1 per cent FeO as total Fe). Biotiteis high in TiO₂ (6?6–7?8 per cent). Ilmenite and titaniferousmagnetite (3?5–10?6 per cent TiO₂) are typically homogeneousgrains; their composition can be expressed in terms of R⁺²RO₃:R⁺²O:R₂⁺³O₄. The intrusion of igneous rocks was probably controlled by subterraneanring fracturing. Subsidence of the country rock within the ringfracture provided space for periodic injections of magma froma lower reservoir up the initial ring fracture to form the BlueMountain rocks at a higher level. Downward movement of the floorof the intrusion during crystallization caused inward slumpingof the cumulates which affected the textural, mineralogical,and chemical evolution of the rocks in different parts of theintrusion. The order of mineral fractionation is reflected by the chemicalvariation in the in situ ultrabasic-gabbroic rocks and the successiveintrusions of titanaugite-ilmenite gabbro and lamprophyre ringdykes, marginal alkali gabbro and lamprophyre dyke swarm. Aninitial decrease, then increase in SiO₂; a steady decrease inMgO, CaO, Ni, and Cr: an initial increase, then decrease inFeO+Fe₂O₃, TiO₂, MnO, and V; almost linear increase in Al₂O₃and late stage increase in alkalis and P₂O₃, implies fractionationof olivine and endiopside, followed by titanaugite and Fe-Tioxides, followed by plagioclase, hornblende, biotite, and apatite.Reversals in the composition of cumulus olivine and endiopsideand Solidification Index, indicate that the ultrabasic-gabbroicsequence is composed of four main injections of magma. The ultrabasic rocks crystallized under conditions of high PH₂Oand fairly high, constant P_O2; P_H2 and P_O2 increased duringthe formation of the gabbroic rocks until fracturing of thechamber roof occurred. The abundance of euhedral amphibole inthe latter injection phases suggests that amphibole accumulatedfrom a hydrous SiO₂ undersaturated magma when an increase inP_O2, stabilized its crystallization. Plutonic complexes similar to Blue Mountain are found withinand beneath the volcanic piles of many oceanic islands, e.g.Canaries, Reunion, and Tahiti, and those intruding thick sedimentarysequences, as at Blue Mountain, e.g. the pipe-like intrusionsof the Monteregian Hills, Quebec.