An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part II: Applications to Degassing

Degassing processes in basaltic magmas rich in both water andcarbon dioxide can be modeled using the solubilities of theendmember systems and the assumption of Henry's law. Suitesof vapor-saturated basaltic melts having a range of initialCO₂/H₂O ratios and erupted over a narrow depth interval willdefine negatively sloped arrays on an H₂O vs CO₂ plot. It isimportant that all of the major volatile species be consideredsimultaneously when interpreting trends in dissolved volatilespecies concentrations in magmas. Based on measured concentrations of water and carbon dioxidein basaltic glasses, the composition of the vapor phase at 1200°Cthat could coexist with a basaltic melt and the pressure atwhich it would be vapor saturated can be calculated. The rangein vapor compositions in equilibrium with submarine basaltsreflects the range in water contents in the melts characteristicof each environment. The ranges in the molar proportion of CO₂in vapor phases (X_CO2) calculated to be in equilibrium withsubmarine tholeiitic glasses are 0•93–1•00 formid-ocean ridge basalts (MORB), 0•60–0•99 forglasses from Kilauea [representative of ocean island basalts(OIB)] and 0–0•94 for glasses from back-arc basins(BABB). MORB glasses from spreading centers ranging from slow(e.g. the Mid-Atlantic Ridge) to fast (e.g. East Pacific Rise,9–13°N) are commonly supersaturated with respect toCO₂-rich vapor, resulting from magma ascent rates so rapid thatmagmas erupt on the sea-floor without having been fully degassedby bubble nucleation and growth during ascent. In contrast tothe MORB glasses, volatile contents in submarine glasses fromKilauea are consistent with having been in equilibrium witha vapor phase containing 60–100 mol% CO₂ at the pressureof eruption, reflecting differences in average magma transportrates during eruptions at mid-ocean ridges and hotspot volcanoes. Degassing during decompression of tholeiitic basaltic magmais characterized by strong partitioning of CO₂ into the vaporphase. During open system degassing, CO₂ is rapidly removedfrom the melt with negligible loss of water, until a pressureis reached at which the melt is in equilibrium with nearly purewater vapor. From this pressure downward, the water contentof the melt follows the water solubility curve. During closedsystem degassing, water and CO₂ contents in vapor-saturatedbasaltic magmas will depend strongly on the vapor compositionas determined by the initial volatile concentrations. Deviationfrom open system behavior, toward lower dissolved H₂O and CO₂saturation concentrations at a given pressure, will be greatestin melts having high total volatile concentrations and highCO₂:H₂O ratios. Closed system degassing of basaltic melts havingthe low initial H₂O and CO₂ contents typical of MORB and OIB,however, are similar to the open system case. KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; degassing     

Fluid Flow During Contact Metamorphism of Ophicarbonate Rocks in the Bergell Aureole, Val Malenco, Italian Alps

Contact-mctamorphic assemblages in ophicarbonate from the Bergellaureole correspond either to model isobaric invariant T-XCO₂points [Atg-Cal-Di-Tr-Fo (6 samples) and Atg-Cal-Tr-Fo-Dol (2)]or to isobaric univariant T-XCO₂, curves [Tr-Cal-Di-Atg (18),Tr-Dol-Atg-Cal (1), Atg-Cal-Fo-Di (1), and Atg-Cal-Tr-Fo (1)].Calcite-dolomite thermometry and mineral-fluid equilibria inthe invariant assemblages record T=440–540C at P=3•5kbar. Equilibrium metamorphic fluids were very H₂O rich withX CO₂,=0•001–0•027. In the invariant assemblagesTr + Fo were produced by prograde decarbonation-dehydrationreactions. In contrast, measured modes and reaction texturesin samples with univariant assemblages indicate thai Tr wasproduced by carbonation reactions. The apparent paradox of simultaneousdecarbonation reactions in the model isobaric invariant assemblagesand carbonation reactions in univariant assemblages is resolvedby local mineral-fluid equilibrium and fluid flow through ophicarbohatesin the direction of decreasing temperature as the aureole heated.Time-integrated flux (q) was computed from measured reactionprogress in 28 samples for models of both horizontal and verticaldown-temperature flow. Results are similar, with q decreasingrapidly from (0•2–5•1) 10⁵ cm³ fluid/cm² rock1•3–1•7 km from the intrusion to 0–0•610⁵cm³/cm² at 1•8–4•0 km. The decrease in q ismore consistent with vertical than horizontal flow. Variationsin time-integrated flux of more than an order of magnitude arerecorded by samples from the same outcrop. The absence of carbonatein adjacent metaperidotite indicates that flow was confinedto the ophicarbonate. Channelized, spatially heterogeneous,vertical flow can be explained by the brecciation and strongvertical foliation of the ophicarbonate relative to surroundingmassive metaperidotite. Generation of metamorphicfluids by decarbonation-dehydrationreactions within the ophicarbonates explains larger averageflux 1–2 km from the intrusion compared with more distalpoints. KEY WORDS: Bergell; contact metamorphism; fluid flow; ophicarbonate ^*Telephone: (410) 516-8121. Fax: (410) 516-7933     

The Distribution of H2O between Cordierite and Granitic Melt: H2O Incorporation in Cordierite and its Application to High-grade Metamorphism and Crustal Anatexis

Experiments defining the distribution of H₂O [D_w = wt % H₂O(melt)/wt% H₂O(crd)]) between granitic melt and coexisting cordieriteover a range of melt H₂O contents from saturated (i.e. coexistingcordierite + melt + vapour) to highly undersaturated (cordierite+ melt) have been conducted at 3–7 kbar and 800–1000°C.H₂O contents in cordierites and granitic melts were determinedusing secondary ion mass spectrometry (SIMS). For H₂O vapour-saturatedconditions D_w ranges from 4·3 to 7 and increases withrising temperature. When the system is volatile undersaturatedD_w decreases to minimum values of 2·6–5·0at moderate to low cordierite H₂O contents (0·6–1·1wt %). At very low aH₂O, cordierite contains less than 0·2–0·3wt % H₂O and D_w increases sharply. The D_w results are consistentwith melt H₂O solubility models in which aH₂O is proportionalto X_w² (where X_w is the mole fraction of H₂O in eight-oxygenunit melt) at X_w     

The Sulfide Capacity and the Sulfur Content at Sulfide Saturation of Silicate Melts at 1400{degrees}C and 1 bar

The solubility of sulfur as S^2– has been experimentallydetermined for 19 silicate melt compositions in the system CaO–MgO–Al₂O₃–SiO₂(CMAS)± TiO₂ ± FeO, at 1400°C and 1 bar, using CO–CO₂–SO₂gas mixtures to vary oxygen fugacity (fO₂) and sulfur fugacity(fS₂). For all compositions, the S solubility is confirmed tobe proportional to (fS₂/fO₂)^1/2, allowing the definition ofthe sulfide capacity (C_S) of a silicate melt as C_S = [S](fO₂/fS₂)^1/2.Additional experiments covering over 150 melt compositions,including some with Na and K, were then used to determine C_Sas a function of melt composition at 1400°C. The resultswere fitted to the equation     

Magmatic Evolution of the La Pacana Caldera System, Central Andes, Chile: Compositional Variation of Two Cogenetic, Large-Volume Felsic Ignimbrites

La Pacana is one of the largest known calderas on Earth, andis the source of at least two major ignimbrite eruptions witha combined volume of some 2700 km³. These ignimbrites have stronglycontrasting compositions, raising the question of whether theyare genetically related. The Toconao ignimbrite is crystal poor,and contains rhyolitic (76–77 wt % SiO₂) tube pumices.The overlying Atana ignimbrite is a homogeneous tuff whose pumiceis dacitic (66–70 wt % SiO₂), dense (40–60% vesicularity)and crystal rich (30–40 % crystals). Phase equilibriaindicate that the Atana magma equilibrated at temperatures of770–790°C with melt water contents of 3·1–4·4wt %. The pre-eruptive Toconao magma was cooler (730–750°C)and its melt more water rich (6·3–6·8 wt% H₂O). A pressure of 200 MPa is inferred from mineral barometryfor the Atana magma chamber. Isotope compositions are variablebut overlapping for both units (⁸⁷Sr/⁸⁶Sr_i 0·7094–0·7131;¹⁴³Nd/¹⁴⁴Nd 0·51222–0·51230) and are consistentwith a dominantly crustal origin. Glass analyses from Atanapumices are similar in composition to those in Toconao tubepumices, demonstrating that the Toconao magma could representa differentiated melt of the Atana magma. Fractional crystallizationmodelling suggests that the Toconao magma can be produced by30% crystallization of the observed Atana mineral phases. Toconaomelt characteristics and intensive parameters are consistentwith a volatile oversaturation-driven eruption. However, thelow H₂O content, high viscosity and high crystal content ofthe Atana magma imply an external eruption trigger. KEY WORDS: Central Andes; crystal-rich dacite; eruption trigger; high-silica rhyolite; zoned magma chamber     

Volatiles in Submarine Basaltic Glasses from the Northern Kerguelen Plateau (ODP Site 1140): Implications for Source Region Compositions, Magmatic Processes, and Plateau Subsidence

Submarine pillow basalts (34 Ma) recovered from the NorthernKerguelen Plateau at ODP Site 1140 contain abundant unalteredglass, providing the first opportunity to measure the volatilecontents of tholeiitic basaltic magmas related to the Kerguelenmantle plume. The glasses have La/Sm and Nb/Zr ratios that varyfrom values similar to Southeast Indian Ridge (SEIR) MORB (Unit1), to slightly more enriched (Unit 6), to values transitionalbetween SEIR MORB and basaltic magmas formed by melting of theKerguelen plume (Units 2 and 3). Volatile contents for glassesin Units 1 and 6 are similar to depleted mid-ocean ridge basalt(MORB) values (0·25–0·27 wt % H₂O, 1240–1450ppm S, 42–54 ppm Cl). In contrast, H₂O contents are higherfor the enriched glasses (Unit 2, 0·44 wt % H₂O; Unit3, 0·69 wt %), as are S (1500 ppm) and Cl (146–206ppm). Cl/K ratios for all glasses are relatively low (0·03–0·04),indicating that assimilation of hydrothermally altered materialdid not occur during shallow-level crystallization. H₂O/Ce forthe enriched glasses (Units 2 and 3) is significantly lowerthan Pacific and South Atlantic MORB values, suggesting thatlow H₂O/Ce may be an inherent characteristic of the Kerguelenplume source. Vapor saturation pressures calculated using theH₂O and CO₂ contents of the glasses indicate that     

Continuous Gradations among Primary Carbonatitic, Kimberlitic, Melilititic, Basaltic, Picritic, and Komatiitic Melts in Equilibrium with Garnet Lherzolite at 3-8 GPa

Multianvil melting experiments in the system CaO–MgO–Al₂O₃–SiO₂–CO₂(CMAS–CO₂) at 3–8 GPa, 1340–1800°C, involvingthe garnet lherzolite phase assemblage in equilibrium with CO₂-bearingmelts, yield continuous gradations in melt composition betweencarbonatite, kimberlite, melilitite, komatiite, picrite, andbasalt melts. The phase relations encompass a divariant surfacein P–T space. Comparison of the carbonatitic melts producedat the low-temperature side of this surface with naturally occurringcarbonatites indicates that natural magnesiocarbonatites couldbe generated over a wide range of pressures >2·5 GPa.Melts analogous to kimberlites form at higher temperatures alongthe divariant surface, which suggests that kimberlite genesisrequires more elevated geotherms. However, the amount of waterfound in some kimberlites has the potential to lower temperaturesfor the generation of kimberlitic melts by up to 150°C,provided no hydrous phases are present. Compositions resemblinggroup IB and IA kimberlites are produced at pressures around5–6 GPa and 10 GPa, respectively, whereas the compositionsof some other kimberlites suggest generation at higher pressuresstill. At pressures <4 GPa, an elevated geotherm producesmelilitite-like melt in the CMAS–CO₂ system rather thankimberlite. Even when a relatively CO₂-rich mantle compositioncontaining 0·15 wt % CO₂ is assumed, kimberlites andmelilitites are produced by <1% melting and carbonatitesare generated by even smaller degrees of melting of <0·5%. KEY WORDS: carbonatite; CO₂; kimberlite; melilitite; melt generation     

Experimental Interaction of Granitic and Basaltic Magmas and Implications for Mafic Enclaves

We have performed time series experiments for periods rangingfrom 3 min to 44 h on the interaction of granite melt and partiallymolten basalt at 920C and 10 kbar, in the presence of 5 wt.%water. With time, the assemblage of the basalt domain changesfrom predominantly amphibole+plagioclase to clinopyroxene+garnet;the melt fraction increases from {small tilde}2•5 to 40%;and between the two domains, the melt compositions progressivelyequilibrate. Initially in each run, melts of the basalt domainhave uniform plateau concentrations for SiO₂, Al₂O₃, CaO, MgO,and FeO because the activities of these components are regulatedby the mineral assemblage, but at advanced stages of reaction,no such control is evident. We have derived analytical expressionsto describe and simulate the diffusion profiles. The concentrationprofiles for SiO₂, Al₂O₃, CaO, and Na₂O in the granite, emanatingfrom the basalt–granite interface, have been used to estimateeffective diffusivities. The values from the shorter runs arecompared with those of the experiment of longest duration forwhich we assumed finite couples in our calculations. In thediffusion calculations for K₂O the difference in melt fractionbetween the two domains is accounted for. The resulting values(in cm²/s) are: D_Na2O=6 10^–7, D_K2O=3 10^–7, D_MgO=9 10^–8, D_CaO=(4–6) 10^–8, and D_SiO2 and D_Al2O3=(3–0•6) 10^–8. They are in reasonable agreement with values fromother studies. On the basis of our experiments we calculatethat mafic enclaves of magmatic origin should equilibrate toa large degree with their host magma in slowly cooling non-convectinggranitic plutons. Enclaves approaching complete re-equilibrationretain distinctly higher modal amounts of mafic minerals. Theydo not compositionally resemble binary magma mixtures, but aremore like host magma with accumulated crystals. We show thatthe modal differences between enclave and host are indicativeof the temperature of homogenization and that, in principle,this temperature can be deduced from equilibrium phase diagrams. ^* Present address: Mineralogisch-Petrologisches Institut, Universitt Gttingen, Goldschmidtstrasse 1, 3400 Gttingen, Germany     

Empirical Solution Model for Alkalic to Tholeiitic Basic Magmas

Currently available models to simulate naturally occurring mineral–meltequilibria use mineral components limited to tholeiitic basaltcompositions and thus they cannot be used for alkali-rick basaltsand basanites. To expand mineral–melt equilibria calculationsto alkali-rich composition space at low pressures, we have derivedequations that describe chemical equilibria between olivine–melt,pyroxene–melt, plagioclase–melt, nepheline–meltand leucite–melt components. Excess free energies of reactionsbetween the end-member mineral and melt components at equilibriumhave been expressed as a function of melt composition, temperatureand fo₂. The database used to calculate the mineral–meltexpressions consists of a total of >350 anhydrous experimentsconducted under controlled oxygen fugacity defined by the quartz–fayalite–magnetite(QFM) oxygen buffer. Rocks used in these experiments range frombasanites, nephelinites and alkali olivine basalts, to tholeiiticbasalts and basaltic andesites. Using bulk compositions of startingmaterials both in this experimental database and in others thatwere not incorporated into the regression of modeled parameters,modeled equations successfully predict, at a given temperatureand fo₂, compositions of multiply saturated melts as well asthe compositions of coexisting minerals. Standard deviationsof the calculated mole fractions of mineral components () areas follows: anorthite 002; forsterite 002; clinoenstatite002; enstatite 0003; nepheline 002; and leucite 001. Standarddeviations () of the calculated melt compositions in terms ofweight percent of oxides are: SiO₂ 0•96; Al₂O₃ 132; Fe₂O₃023; FeO 121; MgO 084; CaO 079; Na₂O 058; and K₂O 069.All calculations were carried out using a non-linear Newton–Raphsonnumerical procedure. KEY WORDS: mineral–melt equilibria; alkalic–tholeiitic basalts; equilibrium thermodynamics ^*Corresponding author     

Formation of Wollastonite by Chemically Reactive Fluid Flow During Contact Metamorphism, Mt. Morrison Pendant, Sierra Nevada, California, USA

Quartz–calcite sandstones experienced the reaction calcite+ quartz = wollastonite + CO₂ during prograde contact metamorphismat P = 1500 bars and T = 560°C. Rocks were in equilibriumduring reaction with a CO₂–H₂O fluid with XCO₂ = 0·14.The transition from calcite-bearing, wollastonite-free to wollastonite-bearing,calcite-free rocks across the wollastonite isograd is only severalmillimeters wide. The wollastonite-forming reaction was drivenby infiltration of quartz–calcite sandstone by chemicallyreactive H₂O-rich fluids, and the distribution of wollastonitedirectly images the flow paths of reactive fluids during metamorphism.The mapped distribution of wollastonite and modeling of an O-isotopeprofile across a lithologic contact indicate that the principaldirection of flow was layer-parallel, directed upward, withany cross-layer component of flow <0·1% of the layer-parallelcomponent. Fluid flow was channeled at a scale of 1–100m by pre-metamorphic dikes, thrust and strike-slip faults, foldhinges, bedding, and stratigraphic contacts. Limits on the amountof fluid, based on minimum and maximum estimates for the displacementof the wollastonite reaction front from the fluid source, are(0·7–1·9) x 10⁵ cm³ fluid/cm² rock. Thesharpness of the wollastonite isograd, the consistency of mineralthermobarometry, the uniform measured ¹⁸O–¹⁶O fractionationsbetween quartz and calcite, and model calculations all arguefor a close approach to local mineral–fluid equilibriumduring the wollastonite-forming reaction. KEY WORDS: contact metamorphism, fluid flow, wollastonite, oxygen isotopes, reaction front     

Experimental and Thermodynamic Constraints on the Sulphur Yield of Peralkaline and Metaluminous Silicic Flood Eruptions

Many basaltic flood provinces are characterized by the existenceof voluminous amounts of silicic magmas, yet the role of thesilicic component in sulphur emissions associated with trapactivity remains poorly known. We have performed experimentsand theoretical calculations to address this issue. The meltsulphur content and fluid/melt partitioning at saturation witheither sulphide or sulphate or both have been experimentallydetermined in three peralkaline rhyolites, which are a majorcomponent of some flood provinces. Experiments were performedat 150 MPa, 800–900°C, fO₂ in the range NNO –2 to NNO + 3 and under water-rich conditions. The sulphur contentis strongly dependent on the peralkalinity of the melt, in additionto fO₂, and reaches 1000 ppm at NNO + 1 in the most stronglyperalkaline composition at 800°C. At all values of fO₂,peralkaline melts can carry 5–20 times more sulphur thantheir metaluminous equivalents. Mildly peralkaline compositionsshow little variation in fluid/melt sulphur partitioning withchanging fO₂ (D_S 270). In the most peralkaline melt, D_S risessharply at fO₂ > NNO + 1 to values of >500. The partitioncoefficient increases steadily for S_bulk between 1 and 6 wt% but remains about constant for S_bulk between 0·5 and1 wt %. At bulk sulphur contents lower than 4 wt %, a temperatureincrease from 800 to 900°C decreases D_S by 10%. These results,along with (1) thermodynamic calculations on the behaviour ofsulphur during the crystallization of basalt and partial meltingof the crust and (2) recent experimental constraints on sulphursolubility in metaluminous rhyolites, show that basalt fractionationcan produce rhyolitic magmas having much more sulphur than rhyolitesderived from crustal anatexis. In particular, hot and dry metaluminoussilicic magmas produced by melting of dehydrated lower crustare virtually devoid of sulphur. In contrast, peralkaline rhyolitesformed by crystal fractionation of alkali basalt can concentrateup to 90% of the original sulphur content of the parental magmas,especially when the basalt is CO₂-rich. On this basis, we estimatethe amounts of sulphur potentially released to the atmosphereby the silicic component of flood eruptive sequences. The peralkalineEthiopian and Deccan rhyolites could have produced 10¹⁷ and10¹⁸ g of S, respectively, which are comparable amounts to publishedestimates for the basaltic activity of each province. In contrast,despite similar erupted volumes, the metaluminous Paraná–Etendekasilicic eruptives could have injected only 4·6 x 10¹⁵g of S in the atmosphere. Peralkaline flood sequences may thushave greater environmental effects than those of metaluminousaffinity, in agreement with evidence available from mass extinctionsand oceanic anoxic events. KEY WORDS: silicic flood eruptions; sulphur; experiment; Ethiopia; Deccan     

Low-Pressure Experimental Constraints on the Evolution of Komatiites

Melting experiments were performed on a komatiitic basalt with17 wt% MgO from Munro Township, Ontario, at I-atm pressure andan oxygen fugacity controlled approximately to the fayalite-magnetite-quartzbuffer. The experiments showed that olivine appears at 1344±5°C,spinel at 1334±6°C plagioclase at 1185±5°C,augite at 1176±5°C and pigeonite at 1154±6°C.Compositionally, olivine varies from Fo₉₀ to Fo₇₄ and displaysan average K^Fe/Mg_D (ol/liq) of 0•32. The spinels are chromitesand chromian spinels with Mg/(Mg + Fe²⁺) ratios between 0•66and 0•;32, which show a marked correlation with meltingtemperature. The pyroxenes show an average K^Fe/Mg_D (px/liq)of 0•26, identical for augite and pigeonite. Plagiodaseranges compositionally between An₈₂ and An₇₂ Plotted in thepseudo-quaternary basalt phase diagram, the liquid line of descentis similar to that observed for quartz tholeiitic magmas. Therefore,the low-pressure, late-stage evolution products of komatiiteand basaltic komatiite parental magmas will chemically and mineralogicallybe ferrobasaltic quartz tholeiites. High-temperature and high-pressuremodeling suggests that the main observed compositional variationof Munro komatiites can be explained by low-pressure crystalfractionation and accumulation of olivine into komatiite liquidswith below 21•5–23•5 wt% MgO and eruptive temperaturesbelow 1435–1465°C for oxygen fugacities between thefayalite-magnetite quartz (FMQ) and iron-wiistite (IW) buffers.The maximum magnesium content of liquid komatiites, assumingequilibrium Fo₉₄ olivine, is 27–29 wt% MgO and eruptivetemperatures are between 1515 and 1540°C. KEY WORDS: komatiites; experimental petrology; Munro Township; Ontario     

Potassic Volcanic Rocks in NE China: Geochemical Constraints on Mantle Source and Magma Genesis

Potassic volcanic rocks from the Wudalianchi, Erkeshan and Keluo(WEK) fields in NE China are located between the Mesozoic SongliaoBasin and the Palaeozoic Xing'am Mountains fold belt. Theserocks erupted during three main eruptive episodes-Miocene (9•6–7•0Ma), Pleistocene (0•56–0•13 Ma) and Recent (AD1719–1721)-and are subdivided into three types-olivineleucitite, leucite basanite and trachybasalt—on the basisof modal composition. In comparison with Cenozoic alkaline basaltsfrom East China that are similar to oceanic island basalts (OIBs),WEK volcanic rocks are lower in Al₂O₃, CaO, Fe₂O3 and Sc, buthigher in K₂O (3•5–7•1 wt %), K₂O/Na₂O (>1)and incompatible elements. High ⁸⁷Sr/⁸⁶Sr (0•7050–0•7056),low ¹⁴³Nd/¹⁴⁴Nd (0•51238–0•51250) and ²⁰⁶Pb/²⁰⁴Pb(17•06–16•61) ratios also distinguish them fromoceanic and Chinese basalts. Trace element and isotope dataindicate that a post-Archaean subcontinental lithospheric mantlesource similar to the postulated EM1 component (enriched mantlewith low ^l43Nd/¹⁴⁴Nd and moderate high ⁸⁷Sr/⁸⁶Sr) must haveplayed a significant role in magma generation. The source rockis considered to be refractory phlogopite-bearing garnet peridotiteheterogeneously enriched in both large ion lithophile elementsand light rare earth elements by ancient metasomatism duringProterozoic times. This source may have mixed recently withOIB-like melts, but has not been modified by subduction of theKula-Pacific plate. Primitive WEK potassic magma was generatedby a low degree of partial melting, initiated by an extensionalphase beginning in the late Tertiary, at pressures of 20–45kbar and in the presence of mixed volatile components of H₂O,CO₂ and halogens. KEY WORDS: potassic volcanic rocks; NE China; geochemistry; montle sourc ^*Corresponding author. Present address: Centre for Petrology and Lithoipheric Studies, School of Earth Sciences, Macquarie University, NSW 2109, Australia     

Metamorphism of Calcic Pelitic Schists, Strafford Dome, Vermont: Compositional Zoning and Reaction History

Four assemblages from calcic pelitic schists from South Strafford,Vermont, have been studied in detail to determine the relationshipbetween reaction history and compositional zoning of minerals.The lowest-grade assemblage is garnet + biotite + chlorite +plagioclase + epidote + quartz + muscovite + graphite + fluid.Along a path of isobaric heating, the net reaction is Chl +Ms + Ep + Gr = Grt + Bt + Pl + fluid. Garnet grows with decreasingFe/(Fe + Mg) and X_Spa, (from 0•2 to 0•05), X_Gra staysnearly constant between 0•20 and 0•25, and plagioclasegrows with X_An increasing from peristerite to 0•2–0•5. The subsequent evolution depends on whether chlorite or epidotereacts out first. If chlorite is removed from the assemblagefirst, the net reaction along an isobaric heating path becomesGrt + Ms + Ep + Qtz + Gr = Bt + Pl + fluid. X_An of plagioclaseincreases to 0•20–0•70, depending on the bulk-rockcomposition and changes in pressure and temperature. If epidoteis removed first, the assemblage becomes a simple pelite andthe net reaction becomes Chl + Pl + Ms + Qtz = Grt + Bt + H₂O.Plagioclase is consumed to provide Ca for growing garnet, andX_An, Fe/(Fe + Mg) of garnet, X_Gra, and X_Spa all decrease. Afterboth chlorite and epidote are removed, continued heating upto the metamorphic peak of {small tilde}600C produces littleprogress of the reaction Grt + Ms = Bt + Pl; and X_An increases. The four assemblages have been numerically modeled using theGibbs method starting with measured compositions. The modelssuccessfully predict the observed compositional zoning and trendsof mineral growth and consumption along the computed P–Tpaths. The models also predict the compositional mineral zoningthat would have resulted from other P–T paths. ^* Present address: Department of Geology, University of Alabama, Tuscaloosa, Alabama 35487     

Experimental Crystallization of Leucogranite Magmas

Both crystallization and melting experiments have been carriedout on two natural, biotite-muscovite (DK) and tourmaline-muscovite(GB) High Himalayan leucogranites (HHL) at 4 kbar, logfO₂ =FMQ–05, aH₂O = 1–0•03, and at five temperaturesbetween 803 and 663C H₂O contents of the quenched glasses wereanalysed by ion microprobe. Plagioclase and biotite are theliquidus phases for reduced melt H₂O contents and H₂O-rich conditions,respectively. H₂O saturation limits range from 8 to 10 wt%.DK has a wider crystallization interval than GB (150 vs 80Cfor conditions close to H₂O saturation), and a slightly higherH₂O-saturated solidus (645 compared with 630C for GB). Tourmalinenever crystallized spontaneously from the melt. Tourmaline seedsalways reacted out to biotite in the biotite-muscovite sample,whereas they remained stable in the tourmaline-muscovite sample.Biotite is replaced by hercynite as the main ferromagnesianphase at high temperature and reduced aH₂O. Muscovite crystallizationis restricted to near-solidus conditions. The compositions ofplagioclase, alkali feldspar, biotite and muscovite are givenas a function of bulk composition, temperature and aH₂O. Glasscompositions are richer in normative quartz than the 4 kbarH₂O-saturated Qz–Ab–Or eutectic, and become moreperaluminous and less mafic with increasing fractionation. Biotitecrystallization in peraluminous liquids is favoured by elevatedFe, Mg and Ti contents. Muscovite crystallization is not promotedunder H₂O-saturated conditions. Tourmaline stability is stronglydependent on aH₂O. For GB, tourmaline is present at elevatedtemperatures for intermediate values of aH₂O (803 C, 0–7),but not above 650C for H₂O-saturated conditions. Comparisonof the natural crystallization sequence with experiments suggestsinitial water contents between 5 and 75 wt % for the DK magma,and > 7 wt% for the GB magma. Plagioclase core compositionsgive minimum temperatures of 700C for GB and 750C for DK,consistent with an emplacement of these HHL as almost entirelyliquid bodies. The restricted occurrence of biotite in the GBgranite suggests that it reacted out during the magmatic evolution,owing to a marked change in fO₂ toward more oxidizing conditions.Tourmaline leucogranites can be generated from biotite leucogranitesby fractional crystallization under conditions of increasingdegree of oxidation. KEY WORDS: leucogranite; melting experiments; crystlization experiments; Himalayas; phase relations ^*Corresponding author     

Intraplutonic Quench Zones in the Kap Edvard Holm Layered Gabbro Complex, East Greenland

The Kap Edvard Holm Layered Gabbro Complex is a large layeredgabbro intrusion (>300 km²) situated on the opposite sideof the Kangerdlugssuaq fjord from the Skaergaard Intrusion.It was emplaced in a continental margin ophiolite setting duringearly Tertiary rifting of the North Atlantic. Gabbroic cumulates, covering a total stratigraphic thicknessof >5 km, have a typical four-phase tholeiitic cumulus mineralogy:plagioclase, clinopyroxene, olivine, and Fe–Ti oxides.The cryptic variation is restricted (plagioclase An_81–51,olivine Fo_85–66, clinopyroxene Wo_43–41 En_46–37Fs_20–11) and there are several reversals in mineral chemistry.Crystallization took place in a low-pressure, continuously fractionatingmagma chamber system which was periodically replenished andtapped. Fine-grained (0•2–0•4 mm) equigranular, thin(0•5–3 m), laterally continuous basaltic zones occurwithin an {small tilde}1000 m thick layered sequence in theTaco Point area. Twelve such zones define the bases of individualmacrorhythmic units with an average thickness of {small tilde}80m. The fine-grained basaltic zones grade upwards, over a fewmetres, into medium-grained (>1 mm) poikilitic, olivine gabbrowith smallscale modal layering. Each fine-grained basaltic zoneis interpreted as an intraplutonic quench zone in which magmachilled against the underlying layered gabbros during influxalong the chamber floor. Supercooling by {small tilde}50C isbelieved to have caused nucleation of plagioclase, olivine,and clinopyroxene in the quench zone. The nucleation rate isbelieved to have been enhanced as the result of in situ crystallizationin a continuously flowing magma. The transition to the overlyingpoikilitic olivine gabbro reflects a decreasing degree of supercooling. Compositional variation in the Taco Point sequence is typicalfor an open magma chamber system: olivine (Fo_{77–68 5})and plagioclase cores (An_80–72) show a zig-zag crypticvariation pattern with no overall systematic trend. Olivinehas the most primitive compositions in the quench zones andmore evolved compositions in the olivine gabbro; plagioclasecores show the opposite trend. Although plagioclase cores arebelieved to retain their original compositions, olivines re-equilibratedby reaction with trapped liquid. Some plagioclase cores containrelatively sodic patches which retain quench compositions. Whole-rock compositions of nine different quench zones varyover a range from 10 to 18% MgO although the mg-number remainsconstant at {small tilde}0•78. The average composition(47•7% SiO₂, 13•3%MgO, 1•57% Na₂O+K₂O) is takenas a best estimate of the parental magma composition, and isequivalent to a high-magnesian olivine tholeiite. The compositionalvariation of the quench zones is believed to reflect burstsof nucleation and growth of olivine and plagioclase during quenching. Magma emplacement is believed to have taken place by separatetranquil influxes which flowed along the interface between alargely consolidated cumulus pile and the residual magma. Theresident magma was elevated with little or no mixing. At certainlevels in the layered sequence the magma drained back into thefeeder system; such a mechanism is referred to as a surge-typemagma chamber system.     

An Experimental Investigation of the Influence of Water and Oxygen Fugacity on Differentiation of MORB at 200 MPa

Crystallization experiments were performed at 200 MPa in thetemperature range 1150–950°C at oxygen fugacitiescorresponding to the quartz–fayalite–magnetite (QFM)and MnO–Mn₃O₄ buffers to assess the role of water andf_O2 on phase relations and differentiation trends in mid-oceanridge basalt (MORB) systems. Starting from a primitive (MgO9·8 wt %) and an evolved MORB (MgO 6·49 wt %),crystallization paths with four different water contents (0·35–4·7wt % H₂O) have been investigated. In primitive MORB, olivineis the liquidus phase followed by plagioclase + clinopyroxene.Amphibole is present only at water-saturated conditions below1000°C, but not all fluid-saturated runs contain amphibole.Magnetite and orthopyroxene are not stable at low f_O2 (QFM buffer).Residual liquids obtained at low f_O2 show a tholeiitic differentiationtrend. The crystallization of magnetite at high f_O2 (MnO–Mn₃O₄buffer) results in a decrease of melt FeO^*/MgO ratio, causinga calc-alkaline differentiation trend. Because the magnetitecrystallization temperature is nearly independent of the H₂Ocontent, in contrast to silicate minerals, the calc-alkalinedifferentiation trend is more pronounced at high water contents.Residual melts at 950°C in a primitive MORB system havecompositions approaching those of oceanic plagiogranites interms of SiO₂ and K₂O, but have Ca/Na ratios and FeO^* contentsthat are too high compared with the natural rocks, implyingthat fractionation processes are necessary to reach typicalcompositions of natural oceanic plagiogranites. KEY WORDS: differentiation; MORB; oxygen fugacity; water activity; oceanic plagiogranite     

Experimental Phase Relations of Water- and Sulfur-Saturated Arc Magmas and the 1982 Eruptions of El Chich?n Volcano

The equilibrium phase relations of two volcanic rocks from thesubduction-related Mexican Volcanic Belt have been determinedwith an argon-pressurized internally heated vessel. One rockis the trachyandesite erupted from El Chich?n Volcano in 1982;the other is a primitive basalt erupted from Jorullo Volcanoin 1759. A simplified synthetic equivalent to the trachyandesitewas also investigated in lesser detail. All charges were saturatedwith hydrous vapor and a sulfur-bearing mineral. Temperatureranged from 800 to 1000?C, pressure from 1 to 4 kb, and f_o2was controlled by four different solid oxygen buffers in a doublegold capsule configuration: fayalite-magnetite-quartz (FMQ),Ni-NiO (NNO), manganosite-hausmanite (MNH), and magnetite-hematite(MTH). Pyrrhotite was the only sulfur-bearing mineral observed in chargesbuffered under FMQ and NNO, whereas anhydrite crystallized underthe more oxidizing MNH or MTH; both of these observations areconsistent with those of earlier workers. With increasing temperatureand pressure, SiO₂ and K₂O decreased in the experimental melts,whereas Al₂O₃ and CaO increased. Sulfur solubility in silicatemelts was low (<0?1 wt% equivalent SO^t₃) for pyrrhotite-saturatedcharges, but significantly greater (to 1?3 wt.% SO^t₃) when anhydritewas present. Sulfur solubility in anhydrite-saturated meltsshowed strong positive dependence on both temperature and P_vapor. Sulfur amounted to some 2?5 wt.% (SO^t₃) of the total ejectaduring the 1982 El Chich?n eruptions, and the original magmaticsulfur content was in the range 1?25–2–5 wt% SO^t₃.Extrapolations of experimental temperature and pressure dependencesfor sulfur solubility indicate that such concentrations couldbe contained in a hydrous, oxidized, basaltic parent melt generatedunder Benioff zone conditions. During ascent through the uppermantle and crust, the sulfur solubility limit of the melt wouldcontinuously decrease; in response, most of the sulfur wouldbe transferred from the melt to anhydrite crystals and a separategas phase. Trachyandesite pumices erupted from El Chich?n in1982 contained both pyrrhotite and anhydrite at a temperatureof 800?C. The composition of the natural pyrrhotite yieldedan f_o2 estimate 1 log unit above the NNO buffer. Based on compositionalvariations in the experimental melts with temperature and pressure,the composition of the matrix glass in the 1982 pumices indicatesequilibration of the magmatic liquid at about P_total=P_vapor=2kb just before eruption. At that time, sulfur in El Chich?ntrachyandesite was about equally partitioned between anhydritemicrophenocrysts and some 20 vol.% gas phase in which H₂S wasprobably the dominant sulfur-bearing species. The melt thencontained only 0?05 wt.% SO^t₃, consistent with experimentalsolubility limits at 800?C and P_vapor=2 kb.     

Formation of Carbon and Hydrogen Species in Magmas at Low Oxygen Fugacity

Studies of iron-bearing silicate melt (ferrobasalt) + iron metallicphase + graphite + hydrogen equilibria show that carbon andhydrogen solubilities in melts are important for the evolutionof the upper mantle. In a series of experiments conducted at3·7 GPa and 1520–1600°C, we have characterizedthe nature (oxidized vs reduced) and quantified the abundancesof C- and H-compounds dissolved in iron-bearing silicate melts.Experiments were carried out in an anvil-with-hole apparatuspermitting the achievement of equal chemical potentials of H₂in the inner Pt capsule and outer furnace assembly. The fO₂for silicate melt–iron equilibrium was 2·32 ±0·04 log units below iron–wüstite (IW). Theferrobasalt used as starting material experienced a reductionof its iron oxides and silicate network. The counterpart wasa liberation of oxygen reacting with the hydrogen entering thecapsule. The amount of H₂O dissolved in the glasses was measuredby ion microprobe and by step-heating and was found to be between1 and 2 wt %. The dissolved carbon content was found to be 1600ppm C by step-heating. The speciation of C and H componentswas determined by IR and Raman spectroscopy. It was establishedthat the main part of the liberated oxygen was used to formOH^– and to a much lesser extent H₂O, and only traces ofH₂, CO₂ and     

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (f_o2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr₂O₃ at a log f_o2= –3 to1?4 wt.% at a log f_o2=–12?8. The Cr²⁺/Cr³⁺ of melt increaseswith decreasing f_o2 and is estimated by assuming a constantpartitioning of Cr³⁺ between chromite and melt at constant temperature.The estimated values of Cr²⁺/Cr³⁺ in the melt are at f_o2 valuesof 4–5 orders of magnitude lower than the equivalent Fe²⁺/Fe³⁺values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of f_o2 below log f_o2=–6.Five experiments at 10 kb indicate that Cr₂O₃ dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at f_o2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al₂O₃ content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.