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     

Mantle-melt Evolution (Dynamic Source) in the Origin of a Single MORB Suite: a Perspective from Magnesian Glasses of Macquarie Island

The effects of source composition and source evolution duringprogressive partial melting on the chemistry of mantle-derivedmid-ocean ridge basalt (MORB) melts were tested using a comprehensivegeochemical and Sr–Nd–Pb isotopic dataset for fresh,magnesian basaltic glasses from the Miocene Macquarie Islandophiolite, SW Pacific. These glasses: (1) exhibit clear parent–daughterrelationships; (2) allow simple reconstruction of primary meltcompositions; (3) show exceptional compositional diversity (e.g.K₂O/TiO₂ 0·09–0·9; La/Yb 1·5–22;²⁰⁶Pb/²⁰⁴Pb 18·70–19·52); (4) preserve changesin major element and isotope compositions, which are correlatedwith the degree of trace element enrichment (e.g. La/Sm). Conventionalmodels for MORB genesis invoke melting of mantle that is heterogeneouson a small scale, followed by binary mixing of variably lithophileelement-enriched melt batches. This type of model fails to explainthe compositions of the Macquarie Island glasses, principallybecause incompatible element ratios (e.g. Nb/U, Sr/Nd) and Pbisotope ratios vary non-systematically with the degree of enrichment.We propose that individual melt batches are produced from instantaneous‘parental’ mantle parageneses, which change continuouslyas melting and melt extraction proceeds. This concept of a ‘dynamicsource’ combines the models of small-scale mantle heterogeneitiesand fractional melting. A dynamic source is an assemblage oflocally equilibrated mantle solids and a related melt fraction.Common MORB magmas that integrate the characteristics of numerousmelt batches therefore tend to conceal the chemical and isotopicidentity of a dynamic source. This study shows that isotoperatios of poorly mixed MORB melts are a complex function ofthe dynamic source evolution, and that the range in isotoperatios within a single MORB suite does not necessarily requiremixing of diverse components. KEY WORDS: mid-ocean ridge basalt; Macquarie Island; radiogenic isotopes; mantle; geochemistry     

Enriched End-member of Primitive MORB Melts: Petrology and Geochemistry of Glasses from Macquarie Island (SW Pacific)

Macquarie Island is an exposure above sea-level of part of thecrest of the Macquarie Ridge. The ridge marks the Australia–Pacificplate boundary south of New Zealand, where the plate boundaryhas evolved progressively since Eocene times from an oceanicspreading system into a system of long transform faults linkedby short spreading segments, and currently into a right-lateralstrike-slip plate boundary. The rocks of Macquarie Island wereformed during spreading at this plate boundary in Miocene times,and include intrusive rocks (mantle and cumulate peridotites,gabbros, sheeted dolerite dyke complexes), volcanic rocks (N-to E-MORB pillow lavas, picrites, breccias, hyaloclastites),and associated sediments. A set of Macquarie Island basalticglasses has been analysed by electron microprobe for major elements,S, Cl and F; by Fourier transform infrared spectroscopy forH₂O; by laser ablation–inductively coupled plasma massspectrometry for trace elements; and by secondary ion mass spectrometryfor Sr, Nd and Pb isotopes. An outstanding compositional featureof the data set (47·4–51·1 wt % SiO₂, 5·65–8·75wt % MgO) is the broad range of K₂O (0·1–1·8wt %) and the strong positive covariation of K₂O with otherincompatible minor and trace elements (e.g. TiO₂ 0·97–2·1%;Na₂O 2·4–4·3%; P₂O₅ 0·08–0·7%;H₂O 0·25–1·5%; La 4·3–46·6ppm). The extent of enrichment in incompatible elements in glassescorrelates positively with isotopic ratios of Sr (⁸⁷Sr/⁸⁶Sr= 0·70255–0·70275) and Pb (²⁰⁶Pb/²⁰⁴Pb =18·951–19·493; ²⁰⁷Pb/²⁰⁴Pb = 15·528–15·589;²⁰⁸Pb/²⁰⁴Pb = 38·523–38·979), and negativelywith Nd (¹⁴³Nd/¹⁴⁴Nd = 0·51310–0·51304).Macquarie Island basaltic glasses are divided into two compositionalgroups according to their mg-number–K₂O relationships.Near-primitive basaltic glasses (Group I) have the highest mg-number(63–69), and high Al₂O₃ and CaO contents at a given K₂Ocontent, and carry microphenocrysts of primitive olivine (Fo_86–89·5).Their bulk compositions are used to calculate primary melt compositionsin equilibrium with the most magnesian Macquarie Island olivines(Fo_90·5). Fractionated, Group II, basaltic glasses aresaturated with olivine + plagioclase ± clinopyroxene,and have lower mg-number (57–67), and relatively low Al₂O₃and CaO contents. Group I glasses define a seriate variationwithin the compositional spectrum of MORB, and extend the compositionalrange from N-MORB compositions to enriched compositions thatrepresent a new primitive enriched MORB end-member. Comparedwith N-MORB, this new end-member is characterized by relativelylow contents of MgO, FeO, SiO₂ and CaO, coupled with high contentsof Al₂O₃, TiO₂, Na₂O, P₂O₅, K₂O and incompatible trace elements,and has the most radiogenic Sr and Pb regional isotope composition.These unusual melt compositions could have been generated bylow-degree partial melting of an enriched mantle peridotitesource, and were erupted without significant mixing with commonN-MORB magmas. The mantle in the Macquarie Island region musthave been enriched and heterogeneous on a very fine scale. Wesuggest that the mantle enrichment implicated in this studyis more likely to be a regional signature that is shared bythe Balleny Islands magmatism than directly related to the hypotheticalBalleny plume itself. KEY WORDS: mid-ocean ridge basalts; Macquarie Island; glass; petrology; geochemistry     

Volatiles in Basaltic Glasses from Loihi Seamount, Hawaii: Evidence for a Relatively Dry Plume Component

New H₂O, CO₂ and S concentration data for basaltic glasses fromLoihi seamount, Hawaii, allow us to model degassing, assimilation,and the distribution of major volatiles within and around theHawaiian plume. Degassing and assimilation have affected CO₂and Cl but not H₂O concentrations in most Loihi glasses. Waterconcentrations relative to similarly incompatible elements inHawaiian submarine magmas are depleted (Loihi), equivalent (Kilauea,North Arch, Kauai–Oahu), or enriched (South Arch). H₂O/Ceratios are uncorrelated with major element composition or extentor depth of melting, but are related to position relative tothe Hawaiian plume and mantle source region composition, consistentwith a zoned plume model. In front of the plume core, overlyingmantle is metasomatized by hydrous partial melts derived fromthe Hawaiian plume. Downstream from the plume core, lavas tapa depleted source region with H₂O/Ce similar to enriched Pacificmid-ocean ridge basalt. Within the plume core, mantle components,thought to represent subducted oceanic lithosphere, have waterenrichments equivalent to (KEA) or less than (KOO) that of Ce.Lower H₂O/Ce in the KOO component may reflect efficient dehydrationof the subducting oceanic crust and sediments during recyclinginto the deep mantle. KEY WORDS: basalt; Hawaii; mantle; plumes; volatiles     

An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part I: Calibration and Solubility Models

Experiments were conducted to determine the solubilities ofH₂O and CO₂ and the nature of their mixing behavior in basalticliquid at pressures and temperature relevant to seqfloor eruption.Mid-ocean ridge basaltic (MORB) liquid was equilibrated at 1200°Cwith pure H₂O at pressures of 176–717 bar and H₂O—CO₂vapor at pressures up to 980 bar. Concentrations and speciationof H₂O and CO₂ dissolved in the quenched glasses were measuredusing IR spectroscopy. Molar absorptivities for the 4500 cm^–1band of hydroxyl groups and the 5200 and 1630 cm^–1 bandsof molecular water are 0•67±0•03, 0•62±0•07,and 25±3 l/mol-cm, respectively. These and previouslydetermined molar absorptivities for a range of silicate meltcompositions correlate positively and linearly with the concentrationof tetrahedral cations (Si+Al). The speciation of water in glass quenched from vapor-saturatedbasaltic melt is similar to that determined by Silver &Stolper (Journal of Petrology 30, 667–709, 1989) in albiticglass and can be fitted by their regular ternary solution modelusing the coefficients for albitic glasses. Concentrations ofmolecular water measured in the quenched basaltic glasses areproportional to f H₂O in all samples regardless of the compositionof the vapor, demonstrating that the activity of molecular waterin basaltic melts follows Henry's law at these pressures. Abest fit to our data and existing higher-pressure water solubilitydata (Khitarov et al., Geochemistry 5, 479–492, 1959;Hamilton et al., Journal of Petrology 5, 21–39, 1964),assuming Henrian behavior for molecular water and that the dependenceof molecular water content on total water content can be describedby the regular solution model, gives estimates for the V^{o, m}_H2Oof 12±1 cm³/mol and for the 1-bar water solubility of0•11 wt%. Concentrations of CO² dissolved as carbonate in the melt forpure CO₂-saturated and mixed H₂O-CO₂-saturated experiments area simple function of f_CO2 These results suggest Henrian behaviorfor the activity of carbonate in basaltic melt and do not supportthe widely held view that water significantly enhances the solutionof carbon dioxide in basaltic melts. Using a V^{o, m}_r of 23 cm³/mol(Pan et al., Geochimica et Cosmochimica Acta 55, 1587–1595,1991), the solubility of carbonate in the melt at 1 bar and1200°C is 0•5 p.p.m. Our revised determination of CO₂solubility is 20% higher than that reported by Stolper &Holloway (Earth and Planetary Science Letters 87, 397–408,1988). KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; experimental petrology     

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     

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     

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     

Crustal origin for coupled 'ultra-depleted' and 'plagioclase' signatures in MORB olivine-hosted melt inclusions: evidence from the Siqueiros Transform Fault,East Pacific Rise

Geochemical data from melt inclusions in olivine phenocrysts in a picritic basalt from the Siqueiros Transform Fault on the northern East Pacific Rise provide insights into the petrogenesis of mid-ocean ridge basalts (MORB). The fresh lava contains ~10% of olivine phenocrysts (Fo_89.3-91.2) and rare, small (<1 mm) plagioclase phenocrysts with subhedral to irregular shapes with a range of compositions (An_80-90, An_57-63). Melt inclusions in olivine phenocrysts are glassy, generally rounded in shape and vary in size from a few to ~200 µm. Although most of the inclusions have compositions that are generally consistent with being representative of parental melts for the pillow-rim glasses, several inclusions are clearly different. One inclusion, which contains a euhedral grain of high-Al, low-Ti spinel, has a composition unlike any melt inclusions previously described from primitive phenocrysts in MORB. It has a very high Al₂O₃ (~20 wt%), very low TiO₂ (~0.04 wt%) and Na₂O (~1 wt%) contents, and a very high CaO/Na₂O value (~14). The glass inclusion is strongly depleted in all incompatible elements (La =0.052 ppm; Yb =0.34; La/Sm(n) ~0.27), but it has large positive Sr and Eu anomalies (Sr/Sr* ~30; Eu/Eu* ~3) and a negative Zr anomaly. It also has low S (0.015 wt%) and relatively high Cl (180 ppm). We suggest that this unusual composition is a consequence of olivine trapping plagioclase in a hot, strongly plagioclase-undersaturated magma and subsequent reaction between plagioclase and the host olivine producing melt and residual spinel. Two other melt inclusions in a different olivine phenocryst have compositions that are generally intermediate between 'normal' inclusions and the aluminous inclusion, but have even higher CaO and Sr contents. They are also depleted in incompatible elements, but to a lesser degree than the aluminous inclusion, and have smaller Sr and Eu anomalies. Similar inclusions have also been described in high-Fo olivine phenocrysts from Iceland and northern Mid-Atlantic Ridge. We suggest that the compositions of these inclusions represent assimilation of gabbroic material into the hot primitive magma. The localised nature of this assimilation is consistent with it occurring within a crystal mush zone where the porosity is high as primitive magmas pass through earlier formed gabbroic 'cumulates'. In such an environment the contaminants are expected to have quite diverse compositions. Although the interaction of primitive melts with gabbroic material may not affect the compositions of erupted MORB melts on a large scale, this process may be important in some MORB suites and should be accounted for in petrogenetic models. Another important implication is that the observed variability in melt inclusion compositions in primitive MORB phenocrysts need not always to reflect processes occurring in the mantle. In particular, inferences on fractional melting processes based on geochemistry of ultra-depleted melt inclusions may not always be valid.     

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     

Phase Relations of Peralkaline Silicic Magmas and Petrogenetic Implications

The phase relationships of three peralkaline rhyolites fromthe Kenya Rift have been established at 150 and 50 MPa, at oxygenfugacities of NNO - 1·6 and NNO + 3·6 (log fO₂relative to the Ni–NiO solid buffer), between 800 and660°C and for melt H₂O contents ranging between saturationand nominally anhydrous. The stability fields of fayalite, sodicamphiboles, chevkinite and fluorite in natural hydrous silicicmagmas are established. Additional phases include quartz, alkalifeldspar, ferrohedenbergite, biotite, aegirine, titanite, montdoriteand oxides. Ferrohedenbergite crystallization is restrictedto the least peralkaline rock, together with fayalite; it isreplaced at low melt water contents by ferrorichterite. Riebeckite–arfvedsoniteappears only in the more peralkaline rocks, at temperaturesbelow 750°C (dry) and below 670°C at H₂O saturation.Under oxidizing conditions, it breaks down to aegirine. In themore peralkaline rocks, biotite is restricted to temperaturesbelow 700°C and conditions close to H₂O saturation. At 50MPa, the tectosilicate liquidus temperatures are raised by 50–60°C,and that of amphibole by 30°C. Riebeckite–arfvedsonitestability extends down nearly to atmospheric pressure, as aresult of its F-rich character. The solidi of all three rocksare depressed by 40–100°C compared with the solidusof the metaluminous granite system, as a result of the abundanceof F and Cl. Low fO₂ lowers solidus temperatures by at least30°C. Comparison with studies of metaluminous and peraluminousfelsic magmas shows that plagioclase crystallization is suppressedas soon as the melt becomes peralkaline, whatever its CaO orvolatile contents. In contrast, at 100 MPa and H₂O saturation,the liquidus temperatures of quartz and alkali feldspar arenot significantly affected by changes in rock peralkalinity,showing that the incorporation of water in peralkaline meltsdiminishes the depression of liquidus temperatures in dry peralkalinesilicic melts compared with dry metaluminous or peraluminousvarieties. At 150 MPa, pre-eruptive melt H₂O contents rangefrom 4 wt % in the least peralkaline rock to nearly 6 wt % inthe two more peralkaline compositions, in broad agreement withprevious melt inclusion data. The experimental results implymagmatic fO₂ at or below the fayalite–quartz–magnetitesolid buffer, temperatures between 740 and 660°C, and meltevolution under near H₂O saturation conditions. KEY WORDS: peralkaline; rhyolite; phase equilibria     

Volcan Popocatepetl, Mexico. Petrology, Magma Mixing, and Immediate Sources of Volatiles for the 1994-Present Eruption

Volcán Popocatépetl has been the site of voluminousdegassing accompanied by minor eruptive activity from late 1994until the time of writing (August 2002). This contribution presentspetrological investigations of magma erupted in 1997 and 1998,including major-element and volatile (S, Cl, F, and H₂O) datafrom glass inclusions and matrix glasses. Magma erupted fromPopocatépetl is a mixture of dacite (65 wt % SiO₂, two-pyroxenes+ plagioclase + Fe–Ti oxides + apatite, 3 wt % H₂O, P= 1·5 kbar, f_O2 = NNO + 0·5 log units) and basalticandesite (53 wt % SiO₂, olivine + two-pyroxenes, 3 wt % H₂O,P = 1–4 kbar). Magma mixed at 4–6 km depth in proportionsbetween 45:55 and 85:15 wt % silicic:mafic magma. The pre-eruptivevolatile content of the basaltic andesite is 1980 ppm S, 1060ppm Cl, 950 ppm F, and 3·3 wt % H₂O. The pre-eruptivevolatile content of the dacite is 130 ± 50 ppm S, 880± 70 ppm Cl, 570 ± 100 ppm F, and 2·9 ±0·2 wt % H₂O. Degassing from 0·031 km³ of eruptedmagma accounts for only 0·7 wt % of the observed SO₂emission. Circulation of magma in the volcanic conduit in thepresence of a modest bubble phase is a possible mechanism toexplain the high rates of degassing and limited magma productionat Popocatépetl. KEY WORDS: glass inclusions; igneous petrology; Mexico; Popocatépetl; volatiles     

Melting of Refractory Mantle at 1{middle dot}5, 2 and 2{middle dot}5 GPa under Anhydrous and H2O-undersaturated Conditions: Implications for the Petrogenesis of High-Ca Boninites and the Influence of Subduction Components on Mantle Melting

Boninites are an important ‘end-member’ supra-subductionzone magmatic suite as they have the highest H₂O contents andrequire the most refractory of mantle wedge sources. The pressure–temperatureconditions of boninite origins in the mantle wedge are importantto understanding subduction zone initiation and subsequent evolution.Reaction experiments at 1·5 GPa (1350–1530°C),2 GPa (1400–1600°C) and 2·5 GPa (1450–1530°C)between a model primary high-Ca boninite magma composition anda refractory harzburgite under anhydrous and H₂O-undersaturatedconditions (2–3 wt % H₂O in the melt) have been completed.The boninite composition was modelled on melt inclusions occurringin the most magnesian olivine phenocrysts in high-Ca boninitesfrom the Northern Tongan forearc and the Upper Pillow Lavasof the Troodos ophiolite. Direct melting experiments on a modelrefractory lherzolite and a harzburgite composition at 1·5GPa under anhydrous conditions (1400–1600°C) havealso been completed. Experiments establish a P, T ‘meltinggrid’ for refractory harzburgite at 1·5, 2 and2·5 GPa and in the presence of 2–3 wt % H₂O. Theeffect of 2–3 wt % dissolved H₂O produces a liquidus depressionin primary boninite of     

The Transition to Potassic Alkaline Volcanism in Island Arcs: The Ringgit--Beser Complex, East Java, Indonesia

The origin of potassic lavas with within-plate characteristicsin island are settings is unclear. The volcanic complex of Ringgit—Beser,situated in eastern Java, has erupted lavas of both normal islandare calc-alkaline type and atypical potassic lavas, includingsome highly magnesian lavas. The occurrence of these primitivelavas gives an unusual insight into the source characteristicsof the potassic lavas. The lavas from Ringgit—Beser have a wide range of K₂O(1.1–6.4 wt. %) and MgO contents (18.0–1.6 wt.%).The most magnesian lavas have high Ni and Cr contents. The calc-alkalinelavas have incompatible trace element patterns typical of islandare lavas with enrichments in large ion lithophile elements(LILE) and light rare earth elements (LREE) relative to highfield strength elements (HFSE) and heavy REE (HREE). The potassiclavas may be divided into two series on the basis of Ba andNb contents, with the enriched potassic (EK) series having higherBa and Nb contents for a given MgO content than the potassic(K) series. The EK and K series lavas have some incompatibletrace element ratios similar to within-plate lavas (e.g., highCe/Pb, low LILE/HFSE ratios, and low B/Be). However, both theEK series and K series lavas have negative Ti and Zr anomalies,and the EK series lavas have high Ba/La similar to are lavas.There is little distinction in Sr and Nd isotopes between theK and EK series, but the calc-alkaline lavas have lower ₈₇Sr/₈₆Srand higher ₁₄₃Nd/₁₄₄Nd ratios than the potassic lavas. The EKseries lavas have lower ₂₀₆Pb/₂₀₄Pb and higher ₂₀₈Pb/₂₀₄Pb thanthe K series lavas, but similar ₂₀₇Pb/₂₀₄Pb ratios. The K serieslavas define an almost horizontal trend in ₂₀₇Pb–₂₀₆Pbspace. The Pb isotopic ratios indicate that the EK series lavasare derived from a single mantle source, whereas the K seriesoriginate from a mixture of two mantle components. Calc-alkalinelavas have Pb isotope ratios similar to other calc-alkalineand tholeiitic lavas from Java, and plot on a mixing line betweenIndian Ocean mid-ocean ridge basalt (MORB) and Indian Oceansediment. Incompatible trace element and Pb isotope data for the calc-alkalinelavas indicate that these lavas have a similar source to othercalc-alkaline lavas erupted in Java, namely melts of the IndianOcean MORB mantle fluxed by fluids from the subducted slab.The potassic lavas originate from enriched mantle sources withinthe wedge which have not been affected by recent subductionprocesses. The EK series lavas are derived from a metasomatizedzone which has EMI-type characteristics. The K series lavasare derived from mixing of melts from Christmas Island-type(EMII) mantle and the metasomatized zone. The metasomatizedzone is probably situated at the base of the lithosphere andthe Indian Ocean MORB and Christmas Island-type mantle componentsare situated in the asthenosphere of the wedge. Isotopic datafor Ringgit—Beser lavas confirm that the mantle wedgeof the Sunda arc is extremely heterogeneous (Foden & Varne,1980; Varne, 1985; Wheller et al., 1987). The similarity in geochemistry between Indonesian potassic lavasand those erupted in continental settings indicates that themagma source is essentially the same, namely a metasomatizedphlogopite-rich layer generated by melts of recycled subductedlithosphere. The lack of negative Ti anomalies in the continentalpotassic lavas is ascribed to lower oxidation states in themantle in continental settings.     

Comparison of major,volatile, and trace element contents in the melts of mid-ocean ridges on the basis of data on inclusions in minerals and quenched glasses of rocks

Using our database on major, trace, and volatile element contents in melt inclusions in minerals and quenched glasses of volcanic rocks reported in the literature, we compared the mean contents of 71 chemical elements in melts from the mid-ocean ridges (MORB) of the Atlantic, Pacific, and Indian oceans and determined the mean MORB composition for all the oceans of the Earth (global MORB composition). Mean ratios of incompatible trace and volatile components (H₂O/Ce, K₂O/Cl, Nb/U, Ba/Rb, Ce/Pb, Nb/U, etc.) were calculated for magmatic melts from all the oceans. Variations of these parameters were estimated, and significant differences between the melts of the Atlantic and Pacific oceans were established.     

A Melt Inclusion Record of Volatiles, Trace Elements and Li-B Isotope Variations in a Single Magma System from the Plat Pays Volcanic Complex, Dominica, Lesser Antilles

Glass inclusions in plagioclase and orthopyroxene from daciticpumice of the Cabrits Dome, Plat Pays Volcanic Complex in southernDominica reveal a complexity of element behavior and Li–Bisotope variations in a single volcanic center that would gounnoticed in a whole-rock study. Inclusions and matrix glassesare high-silica rhyolite with compositions consistent with about50% fractional crystallization of the observed phenocrysts.Estimated crystallization conditions are 760–880°C,200 MPa and oxygen fugacity of FMQ + 1 to +2 log units (whereFMQ is the fayalite–magnetite–quartz buffer). Manyinclusion glasses are volatile-rich (up to 6 wt % H₂O and 2900ppm Cl), but contents range down to 1 wt % H₂O and 2000 ppmCl as a result of shallow-level degassing. Sulfur contents arelow throughout, with <350 ppm S. The trace element compositionof inclusion glasses shows enrichment in light rare earth elements(LREE; (La/Sm)_n = 2·5–6·6) and elevatedBa, Th and K contents compared with whole rocks and similaror lower Nb and heavy REE (HREE; (Gd/Yb)_n = 0·5–1·0).Lithium and boron concentrations and isotope ratios in meltinclusions are highly variable (20–60 ppm Li with ⁷Li= +4 to +15 ± 2; 60–100 ppm B with ¹¹B = +6 to+13 ± 2) and imply trapping of isotopically heterogeneous,hybrid melts. Multiple sources and processes are required toexplain these features. The mid-ocean ridge basalt (MORB)-likeHREE, Nb and Y signature reflects the parental magma(s) derivedfrom the mantle wedge. Positive Ba/Nb, B/Nb and Th/Nb correlationsin inclusion glasses indicate coupled enrichment in stronglyfluid-mobile (Ba, B) and less-mobile (Th, Nb) trace elements,which can be explained by fractional crystallization of plagioclase,orthopyroxene and Fe–Ti oxides. The ⁷Li and ¹¹B valuesare at the high end of known ranges for other island arc magmas.We attribute the high values to a ¹¹B and ⁷Li-enriched slabcomponent derived from sea-floor-altered oceanic crust and possiblyfurther enriched in heavy isotopes by dehydration fractionation.The heterogeneity of isotope ratios in the evolved, trappedmelts is attributed to shallow-level assimilation of older volcanicrocks of the Plat Pays Volcanic Complex. KEY WORDS: subduction; volcanic arcs; igneous processes; melt inclusions; SIMS; trace elements; lithium and boron isotopes; diffusion     

The Origin and Composition of Metasomatic Fluids and Amphiboles beneath Malaita, Solomon Islands

A suite of mantle peridotite xenoliths from the Malaitan alnoitedisplay both trace element enrichment and modal metasomatism.Pargasitic amphibole is present in both garnet- and spinelbearingxenoliths, formed by reaction of a metasomatic fluid (representedby H₂O and Na₂O) with the peridotite assemblage. Two pargasite-formingreactions are postulated, whereby spinel is totally consumed: 6MgAl₂O₄ + 8CaMgSi₂O₆ + 7Mg₂Si₂O₆ + 4H₂O + 2Na₂O = 4NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 6Mg₂SiO₄ or spinel is both a reactant (low Cr) and a product (high Cr): 24MgAlCrO₄ + 16CaMgSi₂O₆ + 14Mg₂Si₂O₆ + 8H₂O + 4Na₂O = 8NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 12MgCr₂O₄ + 12Mg₂SiO₄ Seven garnet—spinel-peridotites display cryptic metasomatismas demonstrated by the LREE enrichment in clinopyroxenes. TheLREE enrichment correlates positively with ¹⁴³ND/¹⁴⁴ND (0?512771–0?513093)which defines a mixing line between a mantle MORB source anda metasomatic fluid. Isotopic evidence (Sr and Nd) from garnet,clinopyroxene, and amphibole demonstrate this fluid has notoriginated in the alnoite sensu stricto. Calculated amphiboleequilibrium liquids show a range in La/Yb and Ce/Yb ratios similarto those calculated for the augite and subcalcic diopside megacrysts.Sr and Nd isotope analyses from amphibole are within error ofthe augite (PHN4074) and subcalcic diopside megacrysts (CRN2I6,PHN4069, and PHN4085). It is concluded that fluids emanatedfrom a proto-alnoite magma throughout megacryst fractionation,and the mixing line was generated during the crystallizationof the subcalcic diopsides. This study demonstrates that metasomatismrepresented in these xenoliths is not a prerequisite for alnoitemagmatism, but is a consequence of it.     

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     

Progressive Low-Grade Metamorphism of a Black Shale Formation, Central Swiss Alps, with Special Reference to Pyrophyllite and Margarite Bearing Assemblages

The unmetamorphosed equivalents of the regionally metamorphosedclays and marls that make up the Alpine Liassic black shaleformation consist of illite, irregular mixed-layer illite/montmorillonite,chlorite, kaolinite, quartz, calcite, and dolomite, with accessoryfeldspars and organic material. At higher grade, in the anchizonalslates, pyrophyllite is present and is thought to have formedat the expense of kaolinite; paragonite and a mixed-layer paragonite/muscovitepresumably formed from the mixed-layer illite/montmorillonite.Anchimetamorphic illite is poorer in Fe and Mg than at the diageneticstage, having lost these elements during the formation of chlorite.Detrital feldspar has disappeared. In epimetamorphic phyllites, chloritoid and margarite appearby the reactions pyrophyllite + chlorite = chloritoid + quartz+ H₂O and pyrophyllite + calcite ± paragonite = margarite+ quartz + H₂O + CO₂, respectively. At the epi-mesozone transition,paragonite and chloritoid seem to become incompatible in thepresence of carbonates and yield the following breakdown products:plagioclase, margarite, clinozoisite (and minor zoisite), andbiotite. The maximum distribution of margarite is at the epizone-mesozoneboundary; at higher metamorphic grade margarite is consumedby a continuous reaction producing plagioclase. Most of the observed assemblages in the anchi-and epizone canbe treated in the two subsystems MgO (or FeO)-Na₂O–CaO–Al₂O₃–(KAl₃O₅–SiO₂–H₂O–CO₂).Chemographic analyses show that the variance of assemblagesdecreases with increasing metamorphic grade. Physical conditions are estimated from calibrated mineral reactionsand other petrographic data. The composition of the fluid phasewas low in X_CO2 throughout the metamorphic profile, whereasX_CH4 was very high, particularly in the anchizone where a_H2Owas probably as low as 0.2. P-T conditions along the metamorphicprofile are 1–2 kb/200–300 °C in the anchizone(Glarus Alps), and 5 kb/500–550 °C at the epi-mesozonetransition (Lukmanier area). Calculated geothermal gradientsdecrease from 50 °C/km in the anchimetamorphic Glarus Alpsto 30 °C/km at the epi-mesozone transition of the Lukmanierarea.     

Heterogeneous mantle melting and magmatic processes at the East Pacific Rise (2.6–3.1°S): Evidence from mid-ocean ridge basalt geochemistry and Sr–Nd–Pb isotopes

ABSTRACT

We present the major and trace elements and Sr, Nd, and Pb isotopes in mid-ocean ridge basalts (MORB) from the East Pacific Rise (EPR) at 2.6–3.1°S. These samples are low-K tholeiites and show significant variation in their major element compositions (e.g. 4.60–8.18 wt% MgO, 8.34–12.12 wt% CaO, 9.78–14.25 wt% Fe₂O₃, and 0.06–0.34 K₂O wt%). Trace element abundances of the 2.6–3.1°S MORB are variably depleted (e.g. (La/Sm), _N = 0.51–0.78, Zr/Y = 2.35–3.42, Th/La = 0.035–0.056, and Ce/Yb = 2.38–3.96) but closely resemble the average N-MORB. In the compatible elements (Ni and Cr) against incompatible element Zr plots, the 2.6–3.1°S MORB show well-defined negative correlations, together with a liquid line of descent (LLD) modelling and petrographic observations, implying a significant role of olivine, plagioclase and clinopyroxene fractionation during magma evolution. When compared to global MORB and peridotites, the 2.6–3.1°S MORB and most of the other axial lavas from the South EPR show similar Zn/Fe, Zn/Mn, and Fe/Mn ratios, attesting to a peridotite-dominated mantle lithology. However, the relationships between incompatible trace element ratios, such as Zr/Rb and Nb/Sm, and the negative correlation between Zr/Nb and ⁸⁷Sr/⁸⁶Sr indicate a geochemically heterogeneous mantle source. The mantle beneath the South EPR likely consists of two components, with the enriched component residing as physically distinct domains (e.g. veins or dikes) in the depleted peridotite matrix. In the Sr–Nd–Pb isotope space, the South EPR MORB lie along the mixing lines between the depleted MORB mantle (DMM) and the ‘C’-like Pukapuka endmember. We infer that low-F melts derived from these enriched materials may cause localized mantle heterogeneity (veins or dikes) via an infiltration process. Subsequent melting of the refertilized mantle may impart an isotopically distinct characteristic to South EPR MORB.