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     

Dissolution of Quartz, Albite, and Orthoclase in H2O-Saturated Haplogranitic Melt at 800{degrees}C and 200 MPa: Diffusive Transport Properties of Granitic Melts at Crustal Anatectic Conditions

We have conducted experiments on dissolution of quartz, albite,orthoclase, and corundum into H₂O-saturated haplogranite meltat 800°C and 200 MPa over a duration of 120–1488 hwith the aim of ascertaining the diffusive transport propertiesof granitic melts at crustal anatectic temperatures. Cylindersof anhydrous starting glass and a single mineral phase (quartzor feldspar) were juxtaposed along flat and polished surfacesinside gold or platinum capsules with 10 wt % added H₂O. Concentrationprofiles in glass (quenched melt) perpendicular to the mineral–glassinterfaces and comparison with relevant phase diagrams suggestthat melts at the interface are saturated in the dissolvingphases after 384 h, and with longer durations the concentrationprofiles are controlled only by diffusion of components in themelt. The evolution of the concentration profiles with timeindicates that uncoupled diffusion in the melt takes place alongthe following four linearly independent directions in oxidecomposition space: SiO₂, Na₂O, and K₂O axes (Si-, Na-, and K-eigenvectors,respectively), and a direction between the Al₂O₃, Na₂O, andK₂O axes (Al-eigenvector), such that the Al/Na molar ratio isequal to that of the bulk melt and the Al/(Na + K) molar ratiois equal to the equilibrium ASI (= mol. Al₂O₃/[Na₂O + K₂O])of the melt. Experiments in which a glass cylinder was sandwichedbetween two mineral cylinders—quartz and albite, quartzand K-feldspar, or albite and corundum—tested the validityof the inferred directions of uncoupled diffusion and exploredlong-range chemical communication in the melt via chemical potentialgradients. The application of available solutions to the diffusionequations for the experimental quartz and feldspar dissolutiondata provides diffusivities along the directions of the Si-eigenvectorand Al-eigenvector of (2·0–2·8) x 10^–15m²/s and (0·6–2·4) x 10^–14 m²/s, respectively.Minimum diffusivities of alkalis [(3–9) x 10^–11m²/s] are orders of magnitude greater than the tetrahedral componentsof the melt. The information provided here determines the rateat which crustal anatexis can occur when sufficient heat issupplied and diffusion is the only mass transport (mixing) processin the melt. The calculated diffusivities imply that a quartzo-feldspathicsource rock with initial grain size of 2–3 mm undergoinghydrostatic, H₂O-saturated melting at 800°C (infinite heatsupply) could produce 20–30 vol. % of homogeneous meltin less than 1–10 years. Slower diffusion in H₂O-undersaturatedmelts will increase this time frame. KEY WORDS: chemical diffusion; haplogranite; mineral dissolution experiments; crustal anatexis     

Coexisting High- and Low-Calcium Melts Identified by Mineral and Melt Inclusion Studies of a Subduction-Influenced Syn-collisional Magma from South Sulawesi, Indonesia

Mineral and melt inclusions in olivines from the most Mg-richmagma from the southern West Sulawesi Volcanic Province indicatethat two distinct melts contributed to its petrogenesis. Thecontribution that dominates the whole-rock composition comesfrom a liquid with high CaO (up to 16 wt %) and low Al₂O₃ contents(CaO/Al₂O₃ up to 1), in equilibrium with spinel, olivine (Fo_85–91;CaO 0·35–0·5 wt %; NiO 0·2–0·30wt %) and clinopyroxene. The other component is richer in SiO₂(>50 wt %) and Al₂O₃ (19–21 wt %), but contains significantlyless CaO (<4 wt %); it is in equilibrium with Cr-rich spinelwith a low TiO₂ content, olivine with low CaO and high NiO content(Fo_90–94; CaO 0·05–0·20 wt %; NiO0·35–0·5 wt %), and orthopyroxene. Boththe high- and low-CaO melts are potassium-rich (>3 wt % K₂O).The high-CaO melt has a normalized trace element pattern thatis typical for subduction-related volcanic rocks, with negativeTa–Nb and Ti anomalies, positive K, Pb and Sr anomalies,and a relatively flat heavy rare earth element (HREE) pattern.The low-CaO melt shows Y and HREE depletion (Gd_n/Yb_n 41), butits trace element pattern resembles that of the whole-rock andhigh-CaO melt in other respects, suggesting only small distinctionsin source areas between the two components. We propose thatthe depth of melting and the dominance of H₂O- or CO₂-bearingfluids were the main controls on generating these contrastingmagmas in a syn-collisional environment. The composition ofthe low-CaO magma does not have any obvious rock equivalent,and it is possible that this type of magma does not easily reachthe Earth's surface without the assistance of a water-poor carriermagma. KEY WORDS: melt inclusions; mineral chemistry; olivine; syn-collisional magmatism; ankaramites; low-Ca magma     

Trace Element and Sr-Pb-Nd-Hf Isotope Evidence for Ancient, Fluid-Dominated Enrichment of the Source of Aldan Shield Lamproites

A phase of Mesozoic extension associated with the terminationof continental collision at the southern margin of the AldanShield produced ultrabasic lamproites in a discontinuous belt500 km long and 150 km wide. The lamproites, locally poorlydiamondiferous, were emplaced as dykes, sills and pipes. AllAldan lamproites have primitive chemical characteristics (e.g.MgO up to 22·7 wt %) and are ultrapotassic (K₂O up to8·3 wt %) and peralkaline with K₂O + Na₂O/Al₂O₃ in therange 0·6–1·16. A distinctive feature ofthese rocks is their low TiO₂ content (0·5–1·4wt %). Aldan lamproites are moderately light rare earth element(LREE) enriched with (La/Yb)_N ranging from 10 to 47. Heavy rareearth element (HREE) abundances are lower than for all otherlamproites by up to a factor of five. Therefore, the combinedmajor and trace element characteristics of the Aldan samplesare not typical of other lamproite occurrences. Large ion lithophileelement concentrations are high (100–800 x Primitive Mantle)but the high field strength elements (HFSE; Nb, Ta, Ti) plusTh and U display unusually low concentrations for rocks of thistype. The style of trace element enrichment recorded by theAldan Shield lamproites is comparable with that of subduction-relatedmagmatism. The Aldan lamproites have among the most extremeinitial isotopic ratios yet recorded from mantle-derived magmas;_Ndi = –10·3 to –22·3, ⁸⁷Sr/⁸⁶Sr_i =0·7055–0·7079, _Hfi = –7·6 to–29·4 and ²⁰⁶Pb/²⁰⁴Pb_i = 16·6–17·4.When interpreted in terms of multi-stage Pb isotope evolution,the Pb isotope data require fractionation from a Bulk Earthreservoir at 3·0 Ga and subsequent evolution with second-stageµ values between 6·4 and 8·0. The inferredArchaean age of the lamproite source is consistent with Nd andHf model ages, which range from 1·5 to 3·0 Ga.Aldan lamproites have _Hf values that range from +3 to –7.Trace element and Sr–Nd–Pb–Hf isotopic ratiosshow coherent variations that suggest that Archaean source enrichmentproduced the negative _Hf as a result of metasomatism by slab-derivedhydrous melts that left rutile–garnet-bearing residua.We conclude that relatively large degrees of partial meltingproduced the lamproites (>5%), which explains the preservationof the isotope–trace element correlations and the lowREE contents. Although high-quality trace element data (e.g.HFSE) are not available for most lamproites, it appears thatmany of their source regions contain a component of recycledoceanic crust, possibly including subducted sediment. The sourcesof the Aldan and many other lamproites are distinct from oceanisland basalt mantle sources. This suggests that the long-termstorage of trace element enriched lamproite sources occurredin the sub-continental lithospheric mantle and not at depthwithin the convecting asthenosphere. KEY WORDS: potassic volcanism; isotope geochemistry; fluid enrichment     

Experimental Petrology of a Highly Potassic Magma

The melting behaviour of a highly potassic biotite mafuriteof the Central African olivine leucitite kindred has been studiedexperimentally as a function of pressure (to 30kb) temperature,and water content (0%, 5%, 15%, 25%, and 40% H₂O). Olivine isthe liquidus phase up to 30 kb for all water contents studiedexcept for anhydrous (clinopyroxene on the liquidus) and 15%H₂O (phlogopite on the liquidus) conditions. Analyses of phasescrystallizing from the biotite mafurite show that pressure hasvery little effect on the composition of clinopyroxene whichis extremely calcium-rich, and low in Al₂O₃ and TiO₂ for allconditions investigated. Phlogopite has low TiO₂ content andtitanphlogopite cannot be a refractory phase in the upper mantlecausing Ti-depletion in partial melts in equilibrium with titanphlogopite.There are apparently no conditions where the extremely potassicbiotite mafurite could be a partial melt from pyrolite but derivationfrom an olivine+clinopyroxene+phlogopite+ilmenite assemblageoccurring as ‘enriched’ patches in the upper mantle,is possible. Liquids in equilibrium with phlogopite as a residualphase at 30 kb would be olivine nephelinites with approximately5% K₂O, Na₂O/K₂O 1 and TiO₂ > 5+. Crystal elutriation withtransported residual phlogopite reacting (phlogopite+liquid1 olivine+liquid 2) at lower pressures provides a mechanismfor K-enrichment and generating Na₂O/K₂O < 1.     

Geochemistry of Picritic and Associated Basalt Flows of the Western Emeishan Flood Basalt Province, China

Picritic lava flows near Lijiang in the late Permian Emeishanflood basalt province are associated with augite-phyric basalt,aphyric basalt, and basaltic pyroclastic units. The dominantphenocryst in the picritic flows is Mg-rich olivine (up to 91·6%forsterite component) with high CaO contents (to 0·42wt %) and glass inclusions, indicating that the olivine crystallizedfrom a melt. Associated chromite has a high Cr-number (73–75).The estimated MgO content of the primitive picritic liquidsis about 22 wt %, and initial melt temperature may have beenas high as 1630–1690°C. The basaltic lavas appearto be related to the picritic ones principally by olivine andclinopyroxene fractionation. Age-corrected Nd–Sr–Pbisotope ratios of the picritic and basaltic lavas are indistinguishableand cover a relatively small range [e.g. _Nd(t) = –1·3to +4·0]. The higher _Nd(t) lavas are isotopically similarto those of several modern oceanic hotspots, and have ocean-island-likepatterns of alteration-resistant incompatible elements. Heavyrare earth element characteristics indicate an important rolefor garnet during melting and that the lavas were formed byfairly small degrees of partial melting. Rough correlationsof isotope ratios with ratios of alteration-resistant highlyincompatible elements (e.g. Nb/La) suggest modest amounts ofcontamination involving continental material or a relativelylow-_Nd component in the source. Overall, our results are consistentwith other evidence suggesting some type of plume-head originfor the Emeishan province. KEY WORDS: Emeishan; flood basalts; picrites; mantle plumes; late Permian     

The Gronnedal-Ika Carbonatite-Syenite Complex, South Greenland: Carbonatite Formation by Liquid Immiscibility

The Grønnedal-Ika complex is dominated by layered nephelinesyenites which were intruded by a xenolithic syenite and a centralplug of calcite to calcite–siderite carbonatite. Aegirine–augite,alkali feldspar and nepheline are the major mineral phases inthe syenites, along with rare calcite. Temperatures of 680–910°Cand silica activities of 0·28–0·43 weredetermined for the crystallization of the syenites on the basisof mineral equilibria. Oxygen fugacities, estimated using titanomagnetitecompositions, were between 2 and 5 log units above the fayalite–magnetite–quartzbuffer during the magmatic stage. Chondrite-normalized REE patternsof magmatic calcite in both carbonatites and syenites are characterizedby REE enrichment (La_CN–Yb_CN = 10–70). Calcite fromthe carbonatites has higher Ba (5490 ppm) and lower HREE concentrationsthan calcite from the syenites (54–106 ppm Ba). This isconsistent with the behavior of these elements during separationof immiscible silicate–carbonate liquid pairs. _Nd(T =1·30 Ga) values of clinopyroxenes from the syenites varybetween +1·8 and +2·8, and _Nd(T) values of whole-rockcarbonatites range from +2·4 to +2·8. Calcitefrom the carbonatites has ¹⁸O values of 7·8 to 8·6and ¹³C values of –3·9 to –4·6. ¹⁸Ovalues of clinopyroxene separates from the nepheline syenitesrange between 4·2 and 4·9. The average oxygenisotopic composition of the nepheline syenitic melt was calculatedbased on known rock–water and mineral–water isotopefractionation to be 5·7 ± 0·4. Nd and C–Oisotope compositions are typical for mantle-derived rocks anddo not indicate significant crustal assimilation for eithersyenite or carbonatite magmas. The difference in ¹⁸O betweencalculated syenitic melts and carbonatites, and the overlapin _Nd values between carbonatites and syenites, are consistentwith derivation of the carbonatites from the syenites via liquidimmiscibility. KEY WORDS: alkaline magmatism; carbonatite; Gardar Province; liquid immiscibility; nepheline syenite     

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.     

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     

Sampling the Cape Verde Mantle Plume: Evolution of Melt Compositions on Santo Antao, Cape Verde Islands

The volcanic history of Santo Antão, NW Cape Verde Islands,includes the eruption of basanite–phonolite series magmasbetween 7·5 and 0·3 Ma and (melilite) nephelinite–phonoliteseries magmas from 0·7 to 0·1 Ma. The most primitivevolcanic rocks are olivine ± clinopyroxene-phyric, whereasthe more evolved rocks have phenocrysts of clinopyroxene ±Fe–Tioxide ± kaersutite ± haüyne ± titanite± sanidine; plagioclase occurs in some intermediate rocks.The analysed samples span a range of 19–0·03% MgO;the most primitive have 37–46% SiO₂, 2·5–7%TiO₂ and are enriched 50–200 x primitive mantle in highlyincompatible elements; the basanitic series is less enrichedthan the nephelinitic series. Geochemical trends in each seriescan be modelled by fractional crystallization of phenocrystassemblages from basanitic and nephelinitic parental magmas.There is little evidence for mineral–melt disequilibrium,and thus magma mixing is not of major importance in controllingbulk-rock compositions. Mantle melting processes are modelledusing fractionation-corrected magma compositions; the modelssuggest 1–4% partial melting of a heterogeneous mantleperidotite source at depths of 90–125 km. Incompatibleelement enrichment among the most primitive magma types is typicalof HIMU OIB. The Sr, Nd and Pb isotopic compositions of theSanto Antão volcanic sequence and geochemical characterchange systematically with time. The older volcanic rocks (7·5–2Ma) vary between two main mantle source components, one of whichis a young HIMU type with ²⁰⁶Pb/²⁰⁴Pb = 19·88, 7/4 =–5, 8/4 0, ⁸⁷Sr/⁸⁶Sr = 0·7033 and ¹⁴³Nd/¹⁴⁴Nd= 0·51288, whereas the other has somewhat less radiogenicSr and Pb and more radiogenic Nd. The intermediate age volcanicrocks (2–0·3 Ma) show a change of sources to two-componentmixing between a carbonatite-related young HIMU-type source(²⁰⁶Pb/²⁰⁴Pb = 19·93, 7/4 = –5, 8/4 = –38,⁸⁷Sr/⁸⁶Sr = 0·70304) and a DM-like source. A more incompatibleelement-enriched component with 7/4 > 0 (old HIMU type) isprominent in the young volcanic rocks (0·3–0·1Ma). The EM1 component that is important in the southern CapeVerde Islands appears to have played no role in the petrogenesisof the Santo Antão magmas. The primary magmas are arguedto be derived by partial melting in the Cape Verde mantle plume;temporal changes in composition are suggested to reflect layeringin the plume conduit. KEY WORDS: radiogenic isotopes; geochemistry; mantle melting; Cape Verde     

Pre-eruptive Conditions of the Huerto Andesite (Fish Canyon System, San Juan Volcanic Field, Colorado): Influence of Volatiles (C-O-H-S) on Phase Equilibria and Mineral Composition

Crystallization experiments at 400 MPa, oxidized condition (logfO₂= NNO + 1, where NNO is nickel–nickel oxide buffer) andover a range of temperatures (850–950°C) and fluidcomposition (XH₂O_in = 0·3–1) have been carriedout to constrain the storage conditions of the sulphur-richmagma of the Huerto Andesite (an anhydrite, pyrrhotite, andS-rich apatite-bearing, post-Fish Canyon Tuff mafic lava). Theresults are used to evaluate the role of fluids released fromthe crystallization of magmas such as the Huerto Andesite onthe remobilization of the largely crystallized dacitic FishCanyon magma body. Experiments were performed using the naturalandesitic bulk composition with and without added sulphur. Thepresence of sulphur slightly affects the phase equilibria bychanging the phase proportions, stability fields of plagioclase,pyroxenes and ilmenite, and also affects the plagioclase composition.Phase equilibria and mineral composition data indicate thatthe magma may have contained 4·5 wt % water in the meltand that the pre-eruptive temperature was 875 ± 25°C.Assuming that the magma was in equilibrium with a fluid phase,the CO₂ concentration of the melt is estimated to be in therange 2000–4000 ppm (at 400 MPa). Before eruption, theandesite had an oxidation state very close to, or slightly within,the co-stability field of anhydrite–pyrrhotite at NNO+ 1·1. At these conditions, the sulphur content in themelt is 500 ppm. Assuming open-system degassing resulting fromcontinuing crystallization at depth, most of the CO₂ dissolvedin the andesitic melt should be released after the crystallizationof <10 vol. % of the magma, corresponding to a cooling from875 to 825–850°C. Thus, the fluids released owingto crystallization processes should be mainly composed of waterat temperatures below 825°C. KEY WORDS: experimental study; andesite; volatile; Fish Canyon Tuff; Huerto Andesite     

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

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

Liquidus Equilibria in the System K2O-Na2O-Al2O3-SiO2-F2O-1-H2O to 100 MPa: I. Silicate-Fluoride Liquid Immiscibility in Anhydrous Systems

Liquidus relations in the four-component system Na₂O–Al₂O₃–SiO₂–F₂O_–1were studied at 0· 1 and 100 MPa to define the locationof fluoride–silicate liquid immiscibility and outlinedifferentiation paths of fluorine-bearing silicic magmas. Thefluoride–silicate liquid immiscibility spans the silica–albite–cryoliteand silica–topaz–cryolite ternaries and the haplogranite-cryolitebinary at greater than 960°C and 0· 1–100 MPa.With increasing Al₂O₃ in the system and increasing aluminum/alkalication ratio, the two-liquid gap contracts and migrates fromthe silica liquidus to the cryolite liquidus. The gap does notextend to subaluminous and peraluminous melt compositions. Forall alkali feldspar–quartz-bearing systems, the miscibilitygap remains located on the cryolite liquidus and is thus inaccessibleto differentiating granitic and rhyolitic melts. In peralkalinesystems, the magmatic differentiation is terminated at the albite–quartz–cryoliteeutectic at 770°C, 100 MPa, 5 wt % F and cation Al/Na =0· 75. The addition of topaz, however, significantlylowers melting temperatures and allows strong fluorine enrichmentin subaluminous compositions. At 100 MPa, the binary topaz–cryoliteeutectic is located at 770°C, 39 wt % F, cation Al/Na 0·95, and the ternary quartz–topaz–cryolite eutecticis found at 740°C, 32 wt % F, 30 wt % SiO₂ and cation Al/Na 0· 95. Such location of both eutectics enables fractionationpaths of subaluminous quartz-saturated systems to produce fluorine-rich,SiO₂-depleted and nepheline-normative residual liquids. KEY WORDS: silicate melt; granite; rhyolite; fluorine; liquid immiscibility     

Experimental Constraints on the Role of Garnet Pyroxenite in the Genesis of High-Fe Mantle Plume Derived Melts

The anhydrous phase relations of an uncontaminated (primitive),ferropicrite lava from the base of the Early Cretaceous Paraná–Etendekacontinental flood basalt province have been determined between1 atm and 7 GPa. The sample has high contents of MgO (14·9wt %), FeO^* (14·9 wt %) and Ni (660 ppm). Olivine phenocrystshave maximum Fo contents of 85 and are in equilibrium with thebulk rock, assuming a of 0·32. A comparison of our results with previous experimental studiesof high-Mg rocks shows that the high FeO content of the ferropicritecauses an expansion of the liquidus crystallization field ofgarnet and clinopyroxene relative to olivine; orthopyroxenewas not observed in any of our experiments. The high FeO contentalso decreases solidus temperatures. Phase relations indicatethat the ferropicrite melt last equilibrated either at 2·2GPa with an olivine–clinopyroxene residue, or at 5 GPawith a garnet–clinopyroxene residue. The low bulk-rockAl₂O₃ content (9 wt %) and high [Gd/Yb]_n ratio (3·1)are consistent with the presence of residual garnet in the ferropicritemelt source and favour high-pressure melting of a garnet pyroxenitesource. The garnet pyroxenite may represent subducted oceaniclithosphere entrained by the upwelling Tristan starting mantleplume head. During adiabatic decompression, intersection ofthe garnet pyroxenite solidus at 5 GPa would occur at a mantlepotential temperature of 1550°C and yield a ferropicriteprimary magma. Subsequent melting of the surrounding peridotiteat 4·5 GPa may be restricted by the thickness of theoverlying sub-continental lithosphere, such that dilution ofthe garnet pyroxenite melt component would be significantlyless than in intra-oceanic plate settings (where the lithosphereis thinner). This model may explain the limited occurrence offerropicrites at the base of continental flood basalt sequencesand their apparent absence in ocean-island basalt successions. KEY WORDS: continental flood basalt; ferropicrite; mantle heterogeneity; mantle melting; phase relations; pyroxenite     

Exhumation History of a Garnet Pyroxenite-bearing Mantle Section from a Continent-Ocean Transition (Northern Apennine Ophiolites, Italy)

Garnet clinopyroxenite and garnet websterite layers occur locallywithin mantle peridotite bodies from the External Liguride Jurassicophiolites (Northern Apennines, Italy). These ophiolites werederived from an ocean–continent transition similar tothe present-day western Iberian margin. The garnet clinopyroxenitesare mafic rocks with a primary mineral assemblage of pyrope-richgarnet + sodic Al-augite (Na₂O 2·5 wt %, Al₂O₃ 12·5wt %), with accessory graphite, Fe–Ni sulphides and rutile.Decompression caused Na-rich plagioclase (An_50–45) exsolutionin clinopyroxene porphyroclasts and extensive development ofsymplectites composed of secondary orthopyroxene + plagioclase(An_85–72) + Al-spinel ± clinopyroxene ±ilmenite at the interface between garnet and primary clinopyroxene.Further decompression is recorded by the development of an olivine+ plagioclase-bearing assemblage, locally under syn-kinematicconditions, at the expense of two-pyroxenes + Al-spinel. Mg-richgarnet has been also found in the websterite layers, which arecommonly characterized by the occurrence of symplectites madeof orthopyroxene + Al-spinel ± clinopyroxene. The enclosingperidotites are Ti-amphibole-bearing lherzolites with a fertilegeochemical signature and a widespread plagioclase-facies myloniticfoliation, which preserve in places a spinel tectonite fabric.Lu–Hf and Sm–Nd mineral isochrons (220 ±13 Ma and 186.0 ± 1·8 Ma, respectively) have beenobtained from a garnet clinopyroxenite layer and interpretedas cooling ages. Geothermobarometric estimates for the high-pressureequilibration have yielded T 1100°C and P 2·8 GPa.The early decompression was associated with moderate cooling,corresponding to T 950°, and development of a spinel tectonitefabric in the lherzolites. Further decompression associatedwith plagioclase–olivine growth in both peridotites andpyroxenites was nearly isothermal. The shallow evolution occurredunder a brittle regime and led to the superposition of hornblendeto serpentine veining stages. The garnet pyroxenite-bearingmantle from the External Liguride ophiolites represents a raretectonic sampling of deep levels of subcontinental lithosphereexhumed in an oceanic setting. The exhumation was probably accomplishedthrough a two-step process that started during Late Palaeozoiccontinental extension. The low-pressure portion of the exhumationpath, probably including also the plagioclase mylonitic shearzones, was related to the Mesozoic (Triassic to Jurassic) riftingthat led to continental break-up. In Jurassic times, the studiedmantle sequence became involved in an extensional detachmentprocess that resulted in sea-floor denudation. KEY WORDS: garnet pyroxenite; ophiolite; non-volcanic margin; mantle exhumation; Sm–Nd and Lu–Hf geochronology     

A Method for Thermodynamical Calculation of Basicity Indicators of Rocks and Minerals

A new method has been suggested for evaluating the overall basicityof minerals and rocks by using ionization reactions involvingone proton: (sum of cations) + H₂O = mineral + H⁺, (sum of cations) + H₂O = (sum of normative minerals of a rock)+ H⁺. The basicity indicators are expressed as standard free energychanges of these reactions (). At standard water pressure (logP_H2O = 0) and chemical activity of the metal ions ( log _Mⁿ⁺= 0), the relationship between and alkalinity of solutions(pH) becomes: = –2.303 RTlog _H⁺ = 2.303 RT pH. The overall basicities of rock-forming oxides, minerals andmajor rocks were calculated from the thermodynamic data on ionsin water solutions and solid compounds.     

Liquidus Equilibria in the System K2O-Na2O-Al2O3-SiO2-F2O-1-H2O to 100 MPa: II. Differentiation Paths of Fluorosilicic Magmas in Hydrous Systems

We investigated phase equilibria in the six-component systemNa₂O–K₂O–Al₂O₃–SiO₂–F₂O_–1–H₂Oat 100 MPa to characterize differentiation paths of naturalfluorine-bearing granitic and rhyolitic magmas. Topaz and cryoliteare stable saturating solid phases in calcium-poor systems.At 100 MPa the maximum solidus depression and fluorine solubilityin evolving silicic melts are controlled by the eutectics haplogranite–cryolite–H₂Oat 640°C and 4 wt % F, and haplogranite–topaz–H₂Oat 640°C and 2 wt % F. Topaz and cryolite form a binaryperalkaline eutectic at 660°C, 100 MPa and fluid saturation.The low-temperature nature of this invariant point causes displacementof multiphase eutectics with quartz and alkali feldspar towardsthe topaz–cryolite join and enables the silicate liquidusand cotectic surfaces to extend to very high fluorine concentrations(more than 30 wt % F) for weakly peraluminous and subaluminouscompositions. The differentiation of fluorine-bearing magmasfollows two distinct paths of fluorine behavior, depending onwhether additional minerals buffer the alkali/alumina ratioin the melt. In systems with micas or aluminosilicates thatbuffer the activity of alumina, magmatic crystallization willreach either topaz or cryolite saturation and the system solidifiesat low fluorine concentration. In leucogranitic suites precipitatingquartz and feldspar only, the liquid line of descent will reachtopaz or cryolite but fluorine will continue to increase untilthe quaternary eutectic with two fluorine-bearing solid phasesis reached at 540°C, 100 MPa and aqueous-fluid saturation.The maximum water solubility in the haplogranitic melts increaseswith the fluorine content and reaches 12· 5 ±0· 5 wt % H₂O at the quartz–cryolite–topazeutectic composition. A continuous transition between hydrousfluorosilicate melts and solute-rich aqueous fluids is not documentedby this study. Our experimental results are applicable to leucocraticfluorosilicic magmas. In multicomponent systems, however, thepresence of calcium may severely limit enrichment of fluorineby crystallization of fluorite. KEY WORDS: granite; rhyolite; topaz; cryolite; magmatic differentiation     

The 1982-83 Eruption at Galunggung Volcano, Java (Indonesia): Oxygen Isotope Geochemistry of a Chemically Zoned Magma Chamber

Mount Galunggung is a historically active volcano in southwesternJava that has erupted four times in the last two centuries.During the most recent event, which occurred during a 9–monthinterval in 1982– 83, some 305 10⁶ m³ of medium–K,calc–alkaline magma was erupted. This eruption was unusualbecause of its duration, the diversity of eruption dynamicsand products, and the range of lava compositions produced. Thecomposition of juvenile material changed gradually during thecourse of the eruption from initial plagioclase (An_60–75)and two–pyrozene bearing andesites with 58% SiO₂ to finalplagioclase (An_85–90), diopside, and olivine (Fo_85–90)bearing primitive magnesium basalts with 47% SiO₂ Mineralogicaland compositional relationships indicate a magmatic evolutioninvolving differentitation of high–Mg parental melt. Theeruptive volumes of 35 10⁶ m³ andesite, 120 10⁶ m³ maficandesite, and 150 10⁶ m³ basalt are consistent with the ideathat the 1982– 83 eruption progressively tapped and draineda magma chamber that had become chemically stratified throughextensive crystal fractionation. Separates of plagioclase and pyroxene have ¹⁸O( SMO W) rangesof + 5. 6 to + 6.0 and + 5.3 to + 5.6, respectively, with ¹⁸O_plag–pxvalues of + 0.4 to + 0.6o, indicating internal O–isotopeequiliburium at temperature of 1100–850 C. The magenesianbasalts have magmatic ¹⁸O/ ¹⁶O ratios similar to those of mid–oceanridge basalt, and the O–isotope ratios of compositionallyevolved derivative melts show no evidence for contaminationof the galunggung magmas by ¹⁸O–rich crust during differentiation.Andesites and transitional mafic and sites have a more variableO–isotope character, with laves and phenocrysts havingboth higher and lower ¹⁸O values than observed in the parentalmagnesium basalts. These features are interpreted to reflectintramagma chamber processes affecting the upper portions ofthe differentiating Galunggung magma body before the 1982–83eruption.     

A New Interpretation of Centimetre-scale Variations in the Progress of Infiltration-driven Metamorphic Reactions: Case Study of Carbonated Metaperidotite, Val d'Efra, Central Alps, Switzerland

Progress () of the infiltration-driven reaction, 4olivine +5CO₂ + H₂O = talc + 5magnesite, that occurred during Barrovianregional metamorphism, varies at the cm-scale by a factor of3·5 within an 3 m³ volume of rock. Mineral and stableisotope compositions record that X_CO2, ¹⁸O_fluid, and ¹³C_fluidwere uniform within error of measurement in the same rock volume.The conventional interpretation of small-scale variations in in terms of channelized fluid flow cannot explain the uniformityin fluid composition. Small-scale variations in resulted insteadbecause (a) reactant olivine was a solid solution, (b) initiallythere were small-scale variations in the amount and compositionof olivine, and (c) fluid composition was completely homogenizedover the same scale by diffusion–dispersion during infiltrationand subsequent reaction. Assuming isochemical reaction, spatialvariations in image variations in the (Mg + Fe)/Si of the parentrock rather than the geometry of metamorphic fluid flow. Ifinfiltration-driven reactions involve minerals fixed in composition,on the other hand, spatial variations in do directly imagefluid flow paths. The geometry of fluid flow can never be determinedfrom geochemical tracers over a distance smaller than the oneover which fluid composition is completely homogenized by diffusion–dispersion. KEY WORDS: Alpine Barrovian metamorphism; diffusion; metamorphic fluid composition; metamorphic fluid flow; reaction progress     

An Experimental Study of the Sulfur Content in Basaltic Melts Saturated with Immiscible Sulfide or Sulfate Liquids at 1300{degrees}C and 1{middle dot}0 GPa

The sulfur content in basaltic melts coexisting with eithersulfide or sulfate melts was determined experimentally. Theexperimental conditions were in the range of 1300–1355°Cand 1·0–1·6 GPa, conditions appropriatefor the melting of the upper mantle above subduction zones.Under these conditions, both sulfide and sulfate were presentas immiscible liquids, as inferred from the round geometriesof the quenched sulfide and sulfate phases. The measured S contentin basaltic melts saturated with sulfate liquids ([S] = 1·5± 0·2 wt %) was 10 times higher than the S contentin basaltic melts saturated with sulfide liquids ([S] = 0·14± 0·02 wt %). In our experiments, sulfate liquidswere stable at fO₂ as low as FMQ = +1·85 [FMQ = log (fO₂)_sample– log (fO₂)_FMQ, where FMQ is the fayalite–magnetite–quartzoxygen buffer], and evidence from other sources indicates thatsulfates will be stable at lower fO₂ in melts with lower activitiesof silica. Because chalcophile and highly siderophile elements,such as Cu, Ni, Au, and Pd, are partitioned preferentially intosulfide phases, melting of sufficiently oxidized sources, inwhich sulfides are not stable, would favor incorporation ofthese elements into the silicate melt produced. Such melts wouldhave a higher potential to generate ore deposits. This studyshows that the high sulfur contents of such oxidized basaltsalso means that relatively small amounts of such magmas canprovide significant amounts of sulfur to exsolving volatilephases and account for the bulk of the sulfur expelled in somevolcanic eruptions, such the 1991 eruption of Mount Pinatubo. KEY WORDS: basalt; mantle; oxidation state; sulfate; sulfur