Chemical evolution of basalts from 23°N along the mid-Atlantic ridge: evidence from melt inclusions

The chemical compositions of melt inclusions in a primitive and an evolved basalt recovered from the mid-Atlantic ridge south of the Kane Fracture Zone (23°–24°N) are determined. The melt inclusions are primitive in composition (0.633–0.747 molar Mg/(Mg+Fe²⁺), 1.01–0.68 wt% TiO₂) and are comparable to other proposed parental magmas except in having higher Al₂O₃ and lower CaO. The primitive melt inclusion compositions indicate that the most primitive magmas erupted in this region are not near primary magma compositions. Olivine and plagioclase microphenocrysts are close to exchange equilibrium with their respective basalt glasses, whose compositions are displaced toward olivine from 1 atm three phase saturation. The most primitive melt inclusion compositions are close to exchange equilibrium with the anorthitic cores of zoned plagioclases (An_78.3-An_83.1; the hosts for the melt inclusions in plagioclase) and with olivines more forsteritic (Fo₈₉-Fo₉₁) than the olivine microphenocrysts (the hosts for the melt inclusions in olivine). Xenocrystic olivine analyzed is Fo₈₉ but contains no melt inclusions. These observations indicate that olivines have exchanged components with the melt after melt inclusion entrapment, whereas plagioclase compositions have remained the same since melt inclusion entrapment. Common denominator element ratio diagrams and oxide versus oxide variation diagrams show that the melt inclusion compositions, which represent liquids higher along the liquid line of descent, are related to the glass compositions by the fractionation of olivine, plagioclase and clinopyroxene (absent from the mincral assemblage), probably occurring at elevated pressures. A model is proposed whereby clinopyroxene segregates from the melt at elevated pressures (to account for its absence in the erupted lavas that have the chemical imprint of clinopyroxene fractionation). Zoned plagioclases in the erupted lavas are thought to be survivors of decompressional melting during magma ascent. Since similar primitive melt inclusions occur in olivine microphenocrysts and in the cores of zoned plagioclases, any model must account for all phases present.     

Hydration vs. oxidation: Modelling implications for Fe–Ti oxide crystallisation in mafic intrusions, with specific reference to the Panzhihua intrusion, SW China

Recent work on the Panzhihua intrusion has produced two separate models for the crystallisation of the intrusion:（1） low-Ti,high CaO and low H₂O（0.5 wt.%） parent magma（equivalent to Emeishan low-Ti basalt） at FMQ;and（2） high-Ti,low CaO and higher H₂O（>1.5 wt.%） parent magma（equivalent to Emeishan high-Ti basalt） at FMQ + 1.5.Modelling of these parent magma compositions produces significantly different results. We present here detailed f（O₂） and H₂O modelling for average compositions of both Emeishan high-Ti and low-Ti ferrobasalts in order to constrain the effects on crystallisation sequences for Emeishan ultra-mafic -mafic layered intrusions.Modelling is consistent with numerous experimental studies on ferro-basaltic magmas from other localities（e.g.Skaergaard intrusion）.Modelling is compared with the geology of the Panzhihua intrusion in order to constrain the crystallisation of the gabbroic rocks and the Fe-Ti oxides ore layers.We suggest that the gabbroic rocks at the Panzhihua intrusion can be best explained by crystallisation from a parent magma similar to that of the high-Ti Emeishan basalt at moderate H₂O contents（0.5-1 wt.%） but at the lower end of TiO₂ content for typical high-Ti basalts（2.5 wt.%TiO₂）. Distinct silicate disequilibrium textures in the Fe-Ti oxide ore layers suggest that an influx of H₂O may be responsible for changing the crystallisation path.An increase in H₂O during crystallisation of gabbroic rocks will result in the depression of silicate liquidus temperatures and resultant disequilibrium with the liquid.Continued cooling of the magma with high H₂O then results in precipitation of Mt-Uv alone. The H₂O content of parent magmas for mafic layered intrusions associated with the ELIP is an important variable.H₂O alters the crystallisation sequence of the basaltic magmas so that at high H₂O and f（O₂） Mt -Uv crystallises earlier than plagioclase and clinopyroxene.Furthermore,the addition of H₂O to an anhydrous magma can explain silicate disequilibrium texture observed in the Fe-Ti oxide ore layers.     

High‐grade metamorphism and partial melting of basic and intermediate rocks

Rocks of basic and intermediate bulk composition occur in orogenic terranes from all geological time periods and are thought to represent significant petrological components of the middle and lower continental crust. However, the former lack of appropriate thermodynamic models for silicate melt, amphibole and clinopyroxene that can be applied to such lithologies at high temperature has inhibited effective phase equilibrium modelling of their petrological evolution during amphibolite‐ and granulite facies metamorphism. In this work, we present phase diagrams calculated in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) compositional system for a range of natural basic and intermediate bulk compositions for conditions of 2–12 kbar and 600–1050 ^°C using newly parameterized activity–composition relationships detailed in a companion paper by Green et al. in this issue. Particular attention is given to mid‐ocean ridge basalt (MORB) and diorite protolith bulk compositions. Calculated subsolidus mineral assemblages in all basic and intermediate rock types are modally dominated by hornblende and plagioclase, with variable proportions of epidote, clinopyroxene, garnet, biotite, muscovite, quartz, titanite or ilmenite present at different pressures. The H₂O‐saturated (wet) solidus has a negative P?T slope and occurs between ～620–690 ^°C at mid‐ to lower‐crustal pressures of 5–10 kbar. The lowest‐T melts generated close to the wet solidus are calculated to have granitic major‐element oxide compositions. Melting at higher temperature is attributed primarily to multivariate hydrate‐breakdown reactions involving biotite and/or hornblende. Partial melt compositions calculated at 800–1050 ^°C for MORB show good correlation with analysed compositions of experimental glasses produced via hydrate‐breakdown melting of natural and synthetic basic protoliths, with Niggli norms indicating that they would crystallize to trondhjemite or tonalite. Diorite is shown to be significantly more fertile than MORB and is calculated to produce high‐T melts (>800 ^°C) of granodioritic composition. Subsolidus and suprasolidus mineral assemblages show no significant variation between different members of the basalt family, although the P?T conditions at which orthopyroxene stabilizes, thus defining the prograde amphibolite–granulite transition, is strongly dependent on bulk‐rock oxidation state and water content. The petrological effects of open‐ and closed‐system processes on the mineral assemblages produced during prograde metamorphism and preserved during retrograde metamorphism are also examined via a case‐study analysis of a natural Archean amphibolite from the Lewisian Complex, northwest Scotland.     

Harzburgite found in the Hegenshan ophiolite,southeastern Central Asian Orogenic Belt: Petrogenesis and geological implications

This paper reports detailed studies on harzburgite and serpentinite in the Hegenshan ophiolitic mélange. Harzburgite consists mainly of olivine and orthopyroxene with trace amounts of clinopyroxene and chromian spinel. Clinopyroxene occurs as isolated crystals or in the intergrowth of chromian spinel–clinopyroxene–orthopyroxene. Harzburgite is moderately to highly depleted, displaying high Fo contents in olivine (90.8–92.2), moderate Al₂O₃ contents in orthopyroxene (1.59–2.79 wt%), low heavy REE abundances in clinopyroxene, and moderate Cr# values of spinel (0.50–0.62). The modal proportions of olivine and orthopyroxene pseudomorph grains imply that the parent of the Hegenshan serpentinite should be harzburgite. Whole-rock compositions of the harzburgite and serpentinite samples are characterized by depletions in Al₂O₃ and CaO and enrichments in light REE, Sr, and U. Geochemical modeling suggests that the Hegenshan harzburgite represents residues after 17–18% partial melting of the primitive mantle. The melt in equilibrium with clinopyroxene is more depleted than typical forearc basalt and boninite. Various pyroxene thermobarometers yield equilibrated temperatures of 945–1067 °C and pressures of 4.8–8.0 kbar for the Hegenshan harzburgite. The oxygen barometer yields results of +0.4 to +1.7 log units above the fayalite–magnetite–quartz buffer for the Hegenshan harzburgite. These petrological and geochemical characteristics, as well as the estimated P–T–fO₂ conditions support a back-arc setting for the Hegenshan ophiolitic mélange.     

The origin of island arc high-alumina basalts

A detailed examination of the hypothesis that high-alumina basalts (HAB) in island arcs are primary magmas derived by 50–60% partial melting of subducted ocean crust eclogite shows that this model is unlikely to be viable. Evidence suggests that the overwhelming majority of arc HAB are porphyritic lavas, enriched in Al₂O₃ either by protracted prior crystallization of olivine and clinopyroxene, or by plagioclase phenocryst accumulation in magmas of basaltic andesite to dacite composition. Experimentally-determined phase relationships of such plagioclase-enriched (non-liquid) compositions have little bearing on the petrogenesis of arc magmas, and do not rule out the possibility that arc HAB can be derived by fractionation of more primitive arc lavas. Although models invoking eclogite-melting can match typical arc HAB REE patterns, calculations indicate that the Ni and Cr contents of proposed Aleutian primary HAB are many times lower than such models predict. In contrast, Ni vs Sc and Cr vs Sc trends for arc HAB are readily explained by olivine (+Cr-sp) and clinopyroxene-dominated fractionation from more primitive arc magmas. GENMIX major element modelling of several HAB compositions as partial melts of MORB eclogite, using appropriate experimentally (26–34 kb)-determined garnet and omphacite compositions yields exceptionally poor matches, especially for CaO, Na₂O, MgO and Al₂O₃. These mismatches are easily explained if the HAB are plagioclase-accumulative. Groundmasses of arc HAB are shown to vary from basaltic andesite to dacite in composition. Crystal fractionation driving liquid compositions toward dacite involves important plagioclase separation, resulting in development of significant negative Eu anomalies in more evolved lavas. Plagioclase accumulation in such evolved liquids tends to diminish or eliminate negative Eu anomalies. Therefore, the absence of positive Eu anomaly in a plagioclase-phyric HAB does not indicate that plagioclase has not accumulated in that lava. In addition, we show that plagioclase phenocrysts in arc HAB are not in equilibrium with the liquids in which they were carried (groundmass). Exceptional volumes of picrite and olivine basalt occur in the Solomons and Vanuatu arcs; the presence in lavas from these and other arcs (Aleutian, Tonga) of olivine phenocrysts to Fo₉₄, finds no ready explanation in the primary eclogite-derived HAB model. We suggest that most lavas in intra-oceanic arcs are derived from parental magmas with >10% MgO; fractionation of olivine (+Cr-sp) and clinopyroxene drives liquids to basalt compositions with <7% MgO, but plagioclase nucleation is delayed by their low but significant (<1%?) H₂O contents. Thus evolved liquid compositions in the basaltic andesite—andesite range may achieve relatively high Al₂O₃ contents (<17.5%). The majority of arc basalts, however, have Al₂O₃ contents in excess of 18%, reflecting plagioclase accumulation. We give new experimental data to show that HAB liquids may be generated by anhydrous, low-degree (<10%) partial melting of peridotite at P<18 kb. Relative to arc HAB, these experimental melts have notably higher Mg#(69–72) and are in equilibrium with olivine Fo_87–89. Only further detailed trace element modelling will show if they might be parental magmas for some arc HAB.     

Deep Fractionation of Clinopyroxene in the East Pacific Rise 13°N: Evidence from High MgO MORB and Melt Inclusions

Mid-ocean ridge basalts (MORBs) from East Pacific Rise (EPR) 13°N are analysed for major and trace elements, both of which show a continuous evolving trend. Positive MgO–Al2O3 and negative MgO–Sc relationships manifest the cotectic crystallization of plagioclase and olivine, which exist with the presence of plagioclase and olivine phenocrysts and the absence of clinopyroxene phenocrysts. However, the fractionation of clinopyroxene is proven by the positive correlation of MgO and CaO. Thus, MORB samples are believed to show a “clinopyroxene paradox”. The highest magnesium-bearing MORB sample E13-3B (MgO=9.52%) is modelled for isobaric crystallization with COMAGMAT at different pressures. Observed CaO/Al2O3 ratios can be derived from E13-3B only by fractional crystallization at pressure >4 ±1 kbar, which necessitates clinopyroxene crystallization and is not consistent with cotectic crystallization of olivine plus plagioclase in the magma chamber (at pressure ~1 kbar). The initial compositions of the melt inclusions, which could represent potential parental magmas, are reconstructed by correcting for post-entrapment crystallization (PEC). The simulated crystallization of initial melt inclusions also produce observed CaO/Al2O3 ratios only at >4±1 kbar, in which clinopyroxene takes part in crystallization. It is suggested that MORB magmas have experienced clinopyroxene fractionation in the lower crust, in and below the Moho transition zone. The MORB magmas have experienced transition from clinopyroxene+plagioclase+olivine crystallization at >4±1 kbar to mainly olivine+plagioclase crystallization at <1 kbar, which contributes to the explanation of the “clinopyroxene paradox”.     

Mineralogy,geochemistry and petrogenesis of the Khopoli mafic intrusion,Deccan Traps,India

The Khopoli intrusion, exposed at the base of the Thakurvadi Formation of the Deccan Traps in the Western Ghats, India, is composed of olivine gabbro with 50–55 % modal olivine, 20–25 % plagioclase, 10–15 % clinopyroxene, 5–10 % low-Ca pyroxene, and <5 % Fe-Ti oxides. It represents a cumulate rock from which trapped interstitial liquid was almost completely expelled. The Khopoli olivine gabbros have high MgO (23.5–26.9 wt.%), Ni (733–883 ppm) and Cr (1,432–1,048 ppm), and low concentrations of incompatible elements including the rare earth elements (REE). The compositions of the most primitive cumulus olivine and clinopyroxene indicate that the parental magma of the Khopoli intrusion was an evolved basaltic melt (Mg# 49–58). Calculated parental melt compositions in equilibrium with clinopyroxene are moderately enriched in the light REE and show many similarities with Deccan tholeiitic basalts of the Bushe, Khandala and Thakurvadi Formations. Nd-Sr isotopic compositions of Khopoli olivine gabbros (εNd_t?=??9.0 to ?12.7; ⁸⁷Sr/⁸⁶Sr?=?0.7088–0.7285) indicate crustal contamination. AFC modelling suggests that the Khopoli olivine gabbros were derived from a Thakurvadi or Khandala-like basaltic melt with variable degrees of crustal contamination. Unlike the commonly alkalic, pre- and post-volcanic intrusions known in the Deccan Traps, the Khopoli intrusion provides a window to the shallow subvolcanic architecture and magmatic processes associated with the main tholeiitic flood basalt sequence. Measured true density values of the Khopoli olivine gabbros are as high as 3.06 g/cm³, and such high-level olivine-rich intrusions in flood basalt provinces can also explain geophysical observations such as high gravity anomalies and high seismic velocity crustal horizons.     

Experimental determination of partition coefficients of ten rare earth elements and barium between clinopyroxene and liquid in the synthetic silicate system at 20 kilobar pressure

Two experiments were carried out at 20 kb pressure for the measurement of partition coefficients of ten lanthanides and barium between diopside clinopyroxene and liquid in the synthetic system diopside-enstatite-silica-H₂O. Starting materials are glass of two different compositions CaMgSi₂O₆ 56, MgSiO₃ 14, SiO₂ 30 weight % and CaMgSi₂O₆ 80, MgSiO₃ 20 weight %.In the experiment on the former composition, the partition coefficient increases regularly with decrease of ionic radii from La to Dy and decreases also regularly from Dy to Lu. In the experiment on the latter composition, stepwise shift of partition coefficient was observed between Dy and Er.The results suggest that the lanthanide cations occupy the site of 8-fold coordination in the clinopyroxene and that the partition coefficients depend on the ionic radii of lanthanide elements and also on the chemical composition of the starting material or heating process during the run.     

Sugarloaf Mountain,central Arizona,USA: A small-scale example of Miocene basalt-rhyolite magma mixing to yield andesitic magmas

Sugarloaf Mountain is a 200-m high volcanic landform in central Arizona, USA, within the transition from the southern Basin and Range to the Colorado Plateau. It is composed of Miocene alkalic basalt (47.2–49.1?wt.% SiO₂; 6.7–7.7?wt.% MgO) and overlying andesite and dacite lavas (61.4–63.9?wt.% SiO₂; 3.5–4.7?wt.% MgO). Sugarloaf Mountain therefore offers an opportunity to evaluate the origin of andesite magmas with respect to coexisting basalt. Important for evaluating Sugarloaf basalt and andesite (plus dacite) is that the andesites contain basaltic minerals olivine (cores Fo_76-86) and clinopyroxene (～Fs_9-18Wo_35-44) coexisting with Na-plagioclase (An_48-28Or_1.4–7), quartz, amphibole, and minor orthopyroxene, biotite, and sanidine. Noteworthy is that andesite mineral textures include reaction and spongy zones and embayments in and on Na-plagioclase and quartz phenocrysts, where some reacted Na-plagioclases have higher-An mantles, plus some similarly reacted and embayed olivine, clinopyroxene, and amphibole phenocrysts.Fractional crystallization of Sugarloaf basaltic magmas cannot alone yield the andesites because their ～61 to 64?wt.% SiO₂ is attended by incompatible REE and HFSE abundances lower than in the basalts (e.g., Ce 77–105 in andesites vs 114–166?ppm in basalts; Zr 149–173 vs 183–237; Nb 21–25 vs 34–42). On the other hand, andesite mineral assemblages, textures, and compositions are consistent with basaltic magmas having mixed with rhyolitic magmas, provided the rhyolite(s) had relatively low REE and HFSE abundances. Linear binary mixing calculations yield good first approximation results for producing andesitic compositions from Sugarloaf basalt compositions and a central Arizona low-REE, low-HFSE rhyolite. For example, mixing proportions 52:48 of Sugarloaf basalt and low incompatible-element rhyolite yields a hybrid composition that matches Sugarloaf andesite well ? although we do not claim to have exact endmembers, but rather, viable proxies. Additionally, the observed mineral textures are all consistent with hot basalt magma mixing into rhyolite magma. Compositional differences among the phenocrysts of Na-plagioclase, clinopyroxene, and amphibole in the andesites suggest several mixing events, and amphibole thermobarometry calculates depths corresponding to 8–16?km and 850° to 980?°C. The amphibole P-T observed for a rather tight compositional range of andesite compositions is consistent with the gathering of several different basalt-rhyolite hybrids into a homogenizing ‘collection' zone prior to eruptions. We interpret Sugarloaf Mountain to represent basalt-rhyolite mixings on a relatively small scale as part of the large scale Miocene (～20 to 15 Ma) magmatism of central Arizona. A particular qualification for this example of hybridization, however, is that the rhyolite endmember have relatively low REE and HFSE abundances.     

Experimental constraints on major and trace element partitioning during partial melting of eclogite

Isobaric partial melting experiments were performed on an Fe-free synthetic composition to simulate partial melting of subducted oceanic crust. Nominally anhydrous experiments at 3.0 GPa yielded melts in equilibrium with garnet (13 to 16 mol.% grossular) and aluminous clinopyroxene (14 to 16 wt.% Al₂O₃). Melt compositions show decreasing Si and alkalis and increasing Ca, Mg, and Ti contents with increasing temperatures. Experiments at 1200 and 1300°C were rutile saturated, whereas experiments at 1400°C contained no residual rutile. We argue that during the initial stages of subduction, accessory rutile is likely to be stable in subsolidus eclogites of average midocean ridge basalt composition and that only large degrees of partial melting will eradicate rutile from an eclogitic source. At 3 GPa, any eclogites with a bulk TiO₂ content of ≥1.5 wt.% rutile will produce rutile-saturated partial melts, except at very high degrees of melting. At higher pressures, all bulk Ti may dissolve in clinopyroxene and garnet, leaving no accessory rutile.Trace element partition coefficients for 24 trace elements between clinopyroxene, garnet, and melt were determined by secondary-ion mass spectrometry analysis of experimental run products at 1400°C and 3 GPa. Partition coefficients for the rare earth elements agree well with previous studies and have been evaluated using the lattice strain model. Partitioning data for high-field strength elements indicate complementary D_Zr/D_Hf for clinopyroxene and garnet. Partial melting of an eclogitic component of different modal compositions may therefore explain both subchondritic and superchondritic Zr/Hf ratios. Superchondritic Zr/Hf has recently been observed in some ocean island basalts (OIB), and this may be taken as further evidence for components of recycled oceanic crust in OIB. The data also indicate slight Nb/Ta fractionation during partial melting of bimineralic eclogite, which is not, however, sufficient to explain some recently observed Nb/Ta fractionation in island arc rocks. Accessory rutile, however, can explain such fractionation.     

Petrogenesis of picrite and associated basalts from the southern Mid-Atlantic Ridge

Basalts dredged from the south wall of a fracture zone transecting the southern Mid-Atlantic Ridge (SMAR) at 54° S are unusual in that they include a suite of highly olivine phyric basalts, sampled along with more normal sparsely plagioclase phyric basalts, and a highly plagioclase phyric basalt. Four basalt types (olivine phyric, sparsely plagioclase phyric, evolved sparsely plagioclase phyric and highly plagioclase phyric) are readily distinguished on the basis of petrography, mineralogy and bulk composition. They range from primitive to evolved, with the olivine phyric basalts having elevated MgO (up to 15.5%) and the plagioclase phyric basalt having elevated Al₂O₃ (19.3%) and CaO (13.1%) contents. Compositional variations are extremely consistant, with the olivine phyric basalts and the sparsely plagioclase phyric basalts defining coherent linear trends. On the basis of the ratios and covariation of the incompatible trace elements Zr, Nb, Y and Ba, distinct parental magmas for each basalt type are required. An investigation of Fe-Mg and Mg-Ni distribution coefficients between olivine and magma indicates that olivines from the olivine phyric basalts are on average too forsteritic and too Ni poor to have crystallized in a magma corresponding to the host bulk rock composition. This implies that these basalts are enriched in xenocrystic olivine. Olivines from the other basalt types are mostly of equilibrium composition, although there are some exceptions. Petrogenetic models for the formation of the different basalt types are quantitatively evaluated in terms of fractional crystallization/crystal accumulation processes. These indicate that (1) the olivine phyric basalts are the products of olivine and minor Cr-spinel accumulation and do not represent analogues of primary magma, or a liquid fractionation trend; (2) that the sparsely plagioclase phyric basalts were formed by polybaric fractional crystallization of olivine, plagioclase and clinopyroxene; and (3) that the evolved sparsely plagioclase phyric basalts are not readily related to one another. The single highly plagioclase phyric basalt is unrelated to the other basalt types and is cumulus enriched in plagioclase.The different basalt types are unrelated to one another and document the presence of at least four distinct magma types erupted in close proximity at this ridge/transform intersection on the southern end of the Mid-Atlantic Ridge.     

Origin of xenoliths in the trachyte at Puu Waawaa,Hualalai Volcano,Hawaii

Rare dunite and 2-pyroxene gabbro xenoliths occur in banded trachyte at Puu Waawaa on Hualalai Volcano, Hawaii. Mineral compositions suggest that these xenoliths formed as cumulates of tholeiitic basalt at shallow depth in a subcaldera magma reservoir. Subsequently, the minerals in the xenoliths underwent subsolidus reequilibration that particularly affected chromite compositions by decreasing their Mg numbers. In addition, olivine lost CaO and plagioclase lost MgO and Fe₂O₃ during subsolidus reequilibration. The xenoliths also reacted with the host trachyte to form secondary mica, amphibole, and orthopyroxene, and to further modify the compositions of some olivine, clinopyroxene, and spinel grains. The reaction products indicate that the host trachyte melt was hydrous. Clinopyroxene in one dunite sample and olivine in most dunite samples have undergone partial melting, apparently in response to addition of water to the xenolith. These xenoliths do not contain CO₂ fluid inclusions, so common in xenoliths from other localities on Hualalai, which suggests that CO₂ was introduced from alkalic basalt magma between the time CO₂-inclusion-free xenoliths erupted at 106±6 ka and the time CO₂-inclusion-rich xenoliths erupted within the last 15 ka.     

Phase relations in transitional and alkali basaltic glasses from Iceland

Basaltic glasses from the three alkalic areas of Iceland (Snaefellsnes Volcanic Zone, Sudurland Volcanic Zone and Vestmannaeyjar Volcanic Area) contain plagioclase, olivine, clinopyroxene, chromian spinel and titanomagnetite as phenocryst phases. The glasses are hypersthene to nepheline normative alkali basaltic with FeO/ MgO ratios between 1.4–4.7. Olivine ranges in composition from Fo₉₀ to Fo₅₅, plagioclase from An₉₀ to An₅₀ and clinopyroxene from En₄₅Fs₁₀Wo₄₅ to En₄₀Fs₁₇Wo₄₃. Clinopyroxene reveals systematic Ti:Al metastable crystallization trends related to the composition of the enclosing glass. Two types of phenocryst are present in most glasses and show a bimodality in size and composition. Microphenocryst phases are those most likely to have crystallized from the enclosing glass, while macrophenocrysts may have crystallized from a liquid of slightly less evolved composition. The glasses show complex phenocryst-glass relations which can be related to a polybaric effect. The normative glass compositions are related to 2-phase cotectic surfaces in the basalt tetrahedron and define the position of the 3-phase cotectic line. In general with increasing FeO/MgO in the glass the phenocryst assemblages vary from clinopyroxene, olivine and plagioclase along a clinopyroxene-olivine surface to olivine and plagioclase along an olivine-plagioclase surface. The normative glass compositions show a deflection from clinopyroxene-bearing to clinopyroxene-free glasses. The appearance of plagioclase together with clinopyroxene and olivine can be explained in the light of experimental investigations of the effect of pressure on phase relations. The major element variation of the glasses is interpreted as representing mantle derived magma batches of primary liquids, modified to some degree by high (6 kbar) and intermediate to low pressure (below 3 kbar) crystal fractionation towards equilibrium phase relations during ascent and residence in crustal magma chambers. The observed deflection in normative compositions of the glasses marks the position of the high pressure 3-phase cotectic line. The bimodality in size and composition of plagioclase and olivine phenocrysts can be related to high pressure crystal fractionation in the melt. The Fe-Ti basalt glasses from Sudurland are believed to be quenched high pressure compositions.     

Evolution of major mineral compositions and trace element abundances during fractional crystallization of a model lunar composition

The evolution of major mineral compositions and trace element abundances during fractional crystallization of a model lunar magma ocean have been calculated. A lunar bulk composition consistent with petrological constraints has been selected. Major mineral compositions have been calculated using published studies of olivine-melt, plagioclase-melt, and pyroxene-olivine equilibria. Trace element abundances have been calculated using experimentally-determined partition coefficients where possible. In the absence of experimental determinations, published partition coefficients obtained by analyzing phase separates from porphyritic volcanic rocks have been used. Trace elements studied are La, Sm, Eu, Lu, Rb, Sr( Eu²⁺), Ni, Co, and Cr.The first mineral to crystallize is olivine, which varies in composition from Fo₉₈ at the liquidus to Fo₉₅ at 50% solidification. Orthopyroxene crystallizes from 50 to 60% solidification with a restricted composition range of En₉₅-En₉₃. Plagioclase and Ca-rich clinopyroxene (X_Wo arbitrarily set equal to 0.5) co-crystallize during the final 40% solidification. Plagioclase changes in composition from An₉₇ to approximately An₉₃, while clinopyroxene evolves from En₄₆ to approximately En₄₀. The concomitant evolution of major element abundances in the melt is also discussed.The concentration of Ni in the melt decreases rapidly because solid-melt partition coefficients are significantly greater than unity at all stages of crystallization. The concentration of Cr in the melt increases slowly during olivine crystallization, then drops precipitously during the crystallization of orthopyroxene and clinopyroxene. The concentration of Co in the melt decreases slowly during olivine and orthopyroxene crystallization, after which it returns slowly to its initial concentration. Rubidium and Sr are not fractionated relative to one another until the onset of plagioclase crystallization. Ratios of Rb/Sr, normalized to their initial concentrations in the magma, do not rise above 10 until 95% of the magma has solidified. The ratios of Eu/Sm and La/Lu, normalized to their initial concentrations in the magma, remain essentially unfractionated until the onset of crystallization of clinopyroxene plus plagioclase, at which point the normalized La/Lu ratio increases to approximately 1.3 at 100% solidification and the normalized Eu/Sm ratio decreases to approximately 0.2 at 100% solidification.The model calculations are used to place approximate constraints on the bulk composition of the primitive Moon. Consideration of the effect on plagioclase composition of the activities of NaO_0.5 and SiO₂ in the melt suggests that the primitive Moon contained less than 0.4 wt % NaO_0.5 and approximately 42–43 wt % SiO₂. Concentrations of the REE in model lunar anorthosites are consistent with the returned samples. Concentrations of the REE in several model ‘highland basalts’ (considered to be representative of the average lunar terrae) are too low when compared with returned samples. Several possible explanations of this discrepancy are considered. The possible role of spinel in a twostage geochemical evolution of mare basalt liquids is discussed.     

An experimental investigation of sub-solidus assemblages formed at high pressure in high-alumina basalt,kyanite eclogite and grosspydite compositions

The sub-solidus fields of crystallization of a spectrum of synthetic aluminous basic compositions (high-alumina basalt, anorthite-enriched high-alumina basalt, kyanite eclogite, grosspydite and gabbroic anorthosite) have been investigated at pressures of up to 36 kb. At low pressures the assemblages are characterized by abundant plagioclase, clinopyroxene and possibly minor olivine and orthopyroxene. These correspond to natural gabbroic and pyroxene granulite assemblages. As pressure is increased garnet appears and increases gradually in amount at the expense of other ferromagnesian minerals and plagioclase, until finally at pressures of >23 kb at 1,100° C, plagioclase disappears and high pressure clinopyroxene+garnet+kyanite±quartz assemblages equivalent to eclogite are obtained. In the eclogite stability field, with further rise in pressure, the ratio ga/cpx and the grossular content of the garnet increase.In the high-alumina basalt composition the transitional garnet granulite assemblage (clinopyroxene+plagioclase+garnet±quartz) is spread over a pressure interval of 11 kb at 1,100° C. This is a greater interval than observed for other basalt compositions and is important in considering the hypothesis that the Mohorovicic Discontinuity is a phase change from basalt to eclogite. It indicates that the change in V _p would be spread over a significant depth range, and no sharp seismic velocity discontinuity could result.The first experimental synthesis of kyanite eclogite from both high-alumina basalt and kyanite eclogite compositions has been obtained, as well as synthesis of unusual grossular-clinopyroxene-kyanite assemblages (grosspydite) from grosspydite and gabbroic anorthosite compositions. The pressures needed to synthesize these assemblages are somewhat greater than the pressures needed to synthesize eclogite from basic compositions of lower alumina content at the same temperature. Experimental confirmation of the observation that there is a direct relation between Gross/Alm + Py ratio of garnet and the Jd/Di ratio of co-existing pyroxene in grosspydite and kyanite eclogite assemblages found in kimberlite pipes has also been obtained.     

Trace element composition of parental magmas from mafic–ultramafic cumulates determined by in situ mineral analyses: The Juquiá mafic–ultramafic alkaline–carbonatite massif,SE Brazil

Major and trace element analyses of relict cores of cumulus minerals (olivine and clinopyroxene) from primitive rocks of the Juquiá mafic–ultramafic alkaline–carbonatite complex (Early Cretaceous) in the Ponta Grossa Arch Alkaline Province, southeastern Brazil, were used to calculate the equilibrium melt compositions. Olivine relict cores are compositionally restricted to the Fo_83–74 interval, and they exhibit significant concentrations of Mn (2220–3001 ppm), Ni (1188–2327 ppm), Ca (175–649 ppm), Co (169–216 ppm), Zn (115–215 ppm), Ti (55–305 ppm), Cr (4–320 ppm) and P (31–154 ppm). Clinopyroxene relict cores are essentially diopside, with minor amounts of hedenbergite and tschermakite components. The trace element contents found in clinopyroxene cores are Ni (196–339 ppm), V (99–318 ppm), Sr (110–260 ppm), Zr (12–163 ppm), Sc (50–78 ppm), P (16–118 ppm), Zn (16–48 ppm) and Co (25–43 ppm). The rare earth element (REE) concentrations are variable (28–240 ppm), with the lighter elements present in the greatest abundance, particularly Ce (up to 83 ppm).The melt compositions in equilibrium with olivine and clinopyroxene cores from different samples suggest that distinct basanite magma batches have played a role in the formation of the Juquiá cumulate rocks. These calculated liquids have compositions that are quite similar to those of the nearby lamprophyre dikes. The CaO/Al₂O₃ values (>0.8) from the lamprophyre dikes and the high La/Zr and low Ti/Eu values from the calculated liquids point to a previous carbonatite metasomatic event in the magmatic source that lead to the formation of wehrlite veins in a peridotitic mantle. The variation in the Hf/Y ratio implies differences in cpx/gt modal proportions in the source. Non-modal mantle batch-melting models indicate that a homogeneous source with little variation in the degree of partial melting cannot explain the trace element differences among the calculated liquids. The models suggest that the geochemical differences represent (1) mixing between metasomatic vein partial melt and garnet lherzolite partial melt and (2) clinopyroxene/garnet modal ratios of the residual mantle.     

Role of melting process and melt–rock reaction in the formation of Jurassic MORB-type basalts (Alpine ophiolites)

This study reports a geochemical investigation of two thick basalt sequences, exposed in the Bracco–Levanto ophiolite (northern Apennine, Italy) and in the Balagne ophiolite (central-northern Corsica, France). These ophiolites are considered to represent an oceanward and a continent-near paleogeographic domain of the Jurassic Liguria–Piedmont basin. Trace elements and Nd isotopic compositions were examined to obtain information about: (1) mantle source and melting process and (2) melt–rock reactions during basalt ascent. Whole-rock analyses revealed that the Balagne basalts are slightly enriched in LREE, Nb, and Ta with respect to the Bracco–Levanto counterparts. These variations are paralleled by clinopyroxene chemistry. In particular, clinopyroxene from the Balagne basalts has higher Ce_N/Sm_N (0.4–0.3 vs. 0.2) and Zr_N/Y_N (0.9–0.6 vs. 0.4–0.3) than that from the Bracco–Levanto basalts. The basalts from the two ophiolites have homogeneous initial Nd isotopic compositions (initial ε_Nd from +?8.8 to +?8.6), within typical depleted mantle values, thereby excluding an origin from a lithospheric mantle source. These data also reject the involvement of contaminant crustal material, as associated continent-derived clastic sediments and radiolarian cherts have a highly radiogenic Nd isotopic fingerprint (ε_Nd at the time of basalt formation?=???5.5 and ??5.2, respectively). We propose that the Bracco–Levanto and the Balagne basalts formed by partial melts of a depleted mantle source, most likely containing a garnet-bearing enriched component. The decoupling between incompatible elements and Nd isotopic signature can be explained either by different degrees of partial melting of a similar asthenospheric source or by reaction of the ascending melts with a lower crustal crystal mush. Both hypotheses are reconcilable with the formation of these two basalt sequences in different domains of a nascent oceanic basin.     

Partial melting of secondary pyroxenite at 1 and 1.5 GPa,and its role in upwelling heterogeneous mantle

We performed partial melting experiments at 1 and 1.5 GPa, and 1180–1400 °C, to investigate the melting under mantle conditions of an olivine-websterite (GV10), which represents a natural proxy of secondary (or stage 2) pyroxenite. Its subsolidus mineralogy consists of clinopyroxene, orthopyroxene, olivine and spinel (+garnet at 1.5 GPa). Solidus temperature is located between 1180 and 1200 °C at 1 GPa, and between 1230 and 1250 °C at 1.5 GPa. Orthopyroxene (±garnet), spinel and clinopyroxene are progressively consumed by melting reactions to produce olivine and melt. High coefficient of orthopyroxene in the melting reaction results in relatively high SiO₂ content of low melt fractions. After orthopyroxene exhaustion, melt composition is controlled by the composition of coexisting clinopyroxene. At increasing melt fraction, CaO content of melt increases, whereas Na₂O, Al₂O₃ and TiO₂ behave as incompatible elements. Low Na₂O contents reflect high partition coefficient of Na between clinopyroxene and melt (\(D_{{{\text{Na}}_{ 2} {\text{O}}}}^{{{\text{cpx}}/{\text{liquid}}}}\)). Melting of GV10 produces Quartz- to Hyperstene-normative basaltic melts that differ from peridotitic melts only in terms of lower Na₂O and higher CaO contents. We model the partial melting of mantle sources made of different mixing of secondary pyroxenite and fertile lherzolite in the context of adiabatic oceanic mantle upwelling. At low potential temperatures (T _P < 1310 °C), low-degree melt fractions from secondary pyroxenite react with surrounding peridotite producing orthopyroxene-rich reaction zones (or refertilized peridotite) and refractory clinopyroxene-rich residues. At higher T _P (1310–1430 °C), simultaneous melting of pyroxenite and peridotite produces mixed melts with major element compositions matching those of primitive MORBs. This reinforces the notion that secondary pyroxenite may be potential hidden components in MORB mantle source.     

Clinopyroxene + liquid equilibria to 100 kbar and 2450 K

One of the most active issues in igneous petrology is the investigation of mantle melting, and subsequent differentiation. To evaluate alternative hypotheses for melting and differentiation it is essential to accurately predict clinopyroxene compositions in natural systems. Expressions have thus been derived that describe clinopyroxene-melt equilibria, and allow equilibrium clinopyroxene compositions to be calculated. These equations were constructed from least-squares regression analysis of experimental clinopyroxene-liquid pairs. The calibration database included clinopyroxenes synthesized from both natural and synthetic basalt compositions; experimental conditions ranged from 0 to 100 kbar and 1350 to 2450 K. Regression equations were based on thermodynamic functions. Empirical expressions were also derived, since such models yield more precise estimates of clinopyroxene compositions, and may be easily incorporated into existing liquid line-of-descent models. Such equations may be useful for calculation of high pressure liquid fractionation, or for constraining P-T conditions for basalts produced by partial melting of a pyroxene-bearing source. Models of mantle melting often rely on expressions involving simple element ratios. Partition coefficients (K _d ^cpx/liq ) for the minor elements, Na and Ti, were thus also calibrated as a function of P, T and composition. K _Ti ^cpx/liq , while sensitive to composition was relatively insensitive to P and T. In contrast, K _Na ^cpx/liq increases substantially with increasing P, and exceeded 1 in some experiments. Since oceanic basalts show variations in Na/Ti ratios, the potential exists for partial melting depths to be inferred from K _Na ^cpx/liq . Received: 28 May 1997 / Accepted: 20 November 1998     

Rare earth element partitioning between clinopyroxene and silicate liquid at moderate to high pressure

Experimental determination of over seventy sets of clinopyroxene/silicate liquid (glass) partitition coefficients (D) for four rare earth elements (REE — La, Sm, Ho, Lu) in a range of REE-enriched natural rock compositions (basalt, basaltic andesite, andesite and rhyodacite) demonstrate a convex upward pattern, favouring the heavy REE (Ho, Lu) and markedly discriminating against the light REE (La). These patterns are consistent with previously documented clinopyroxene D values reported from natural phenocryst/matrix pairs and from experimental work using either REE-enriched compositions and electron microprobe analytical techniques (as in the present study) or natural or synthetic undoped compositions and mass spectrometric, ion probe or X-ray autoradiographic analytical techniques. However, the large data base in the present study allows evaluation of the effect of compositional and physical parameters on REE partitioning relationships. Considering D_Ho, it is shown that (1) D increases 6-fold with increasing SiO₂ content of the coexisting liquid from 50 to 70 wt% SiO₂ (2) D increases 4-fold with decreasing temperature from 1,120°C to 900° C (3) D increases 2-fold with increasing pressure from 2.5 to 20 kb. (4) D increases 2-fold fO₂ increases from approximately that of the MW buffer to the HM buffer (5) D remains unchanged within experimental error as the water content of the melt changes from 0.3 to 10% by weight H₂O.The absolute REE content of the clinopyroxene shows no consistent trend with temperature, but decreases slightly with increasing pressure, paralleling an increase in the jadeite component of the pyroxene. Thus the increase in D with increasing pressure is attributed to changes in the silicate liquid structure, which discriminate against accommodation of REE with increasing pressure. The clinopyroxene REE content increases with increasing fO₂, and in this case the increase in D with increasing fO₂ may be attributed mainly to this change in the clinopyroxene composition. Application of the present results to geochemical modelling allows a more appropriate choice of D values, according to the liquid composition and physical conditions applicable in the modelled system. They may also be used to evaluate cognate or xenocrystic relationships between clinopyroxene megacrysts and their host matrix.