Paragenetic relations of diamond with silicate and carbonate minerals in the carbonatite-diamond system: Experiments at 8.5 GPa

Phase relations of diamond and syngenetic minerals were experimentally investigated in the multicomponent system natural carbonatite-diamond at a pressure of 8.5 GPa and temperatures of 1300–1800°C (within the thermodynamic stability field of diamond). Under such conditions, the natural carbonatite of the Chagatai complex (Uzbekistan) acquires the mineralogy of Ca-rich eclogites (grospydites). The melting phase diagram of this system (syngenesis diagram) was constructed; an important element of this diagram is the diamond solubility curve in completely miscible carbonate-silicate melts (solubility values are 15–18 wt % C). The diamond solubility curve divides the phase diagram into two fields corresponding to (1) phase relations involving diamond-undersaturated melts-solutions of carbon with garnet as a liquidus phase (region of diamond dissolution) and (2) phase relations with diamond-saturated melts-solutions with diamond as a liquidus phase (region of diamond crystallization). During a temperature decrease in the region of diamond crystallization from carbonate-silicate melts, the crystallization of diamond is accompanied by the sequential formation of the following phase assemblages: diamond + garnet + melt, diamond + garnet + clinopyroxene + melt, and diamond + garnet + clinopyroxene + carbonate + melt, and the subsolidus assemblage diamond + garnet + clinopyroxene + carbonate is eventually formed. This is indicative of the paragenetic nature of silicate and carbonate minerals co-crystallizing with diamond and corresponding primary inclusions trapped by the growing diamond. A physicochemical mechanism was proposed for the formation of diamond in carbonate-silicate melts. The obtained results were used to analyze the physicochemical behavior of a natural diamond-forming magma chamber.     

Melt evolution during the crystallization of basanites of the Tergesh pipe,northern Minusinsk Depression

In this paper we describe the mineralogy and geochemistry of basanites and melt inclusions in minerals from the Tergesh pipe, northern Minusinsk Depression. The rocks are composed of olivine and clinopyroxene phenocrysts and a groundmass of olivine, clinopyroxene, titanomagnetite, plagioclase, apatite, ilmenite, and glass. Melt inclusions were found only in the olivine and clinopyroxene phenocrysts. Primary melt inclusions in olivine contain glass, rh?nite, clinopyroxene, a sulfide globule, and low-density fluid. The phase composition of melt inclusions in clinopyroxene is glass + low-density fluid ± xenogenous magnetite. According to thermometric investigations, the olivine phenocrysts began crystallizing at T = 1280–1320°C and P > 3.5 kbar, whereas groundmass minerals were formed under near-surface conditions at T ≤ 1200°C. The oxygen fugacity gradually changed during basanite crystallization from oxidizing (NNO) to more reducing conditions (QFM). The investigation of glass compositions (heated and unheated inclusions in phenocrysts and groundmass) showed that the evolution of a basanite melt during its crystallization included mainly an increase in SiO₂, Al₂O₃, and alkalis, while a decrease in femic components, and the melt composition moved gradually toward tephriphonolite and trachyandesite. Geochemical evidence suggests that the primary basanite melt was derived from a mantle source affected by differentiation. Original Russian Text ? T.Yu. Timina, V.V. Sharygin, A.V. Golovin, 2006, published in Geokhimiya, 2006, No. 8, pp. 814–833.     

The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism

The Finero peridotite massif is a harzburgite that suffered a dramatic metasomatic enrichment resulting in the pervasive presence of amphibole and phlogopite and in the sporadic occurrence of apatite and carbonate (dolomite)-bearing domains. Pyroxenite (websterite) dykes also contain phlogopite and amphibole, but are rare. Peridotite bulk-rock composition retained highly depleted major element characteristics, but was enriched in K, Rb, Ba, Sr, LREE (light rare earth elements) (La_N/Yb_N = 8–17) and depleted in Nb. It has high radiogenic Sr (⁸⁷Sr/⁸⁶Sr₍₂₇₀₎ = 0.7055–0.7093), low radiogenic Nd (ɛNd₍₂₇₀₎= −1 to −3) and EMII-like Pb isotopes. Two pyroxenite – peridotite sections examined in detail show the virtual absence of major and trace element gradients in the mineral phases. In both rock types, pyroxenes and olivines have the most unfertile major element composition observed in Ivrea peridotites, spinels are the richest in Cr, and amphibole is pargasite. Clinopyroxenes exhibit LREE-enriched patterns (La_N/Yb_N ∼16), negative Ti and Zr and generally positive Sr anomaly. Amphibole has similar characteristics, except a weak negative Sr anomaly, but incompatible element concentration ∼1.9 (Sr) to ∼7.9 (Ti) times higher than that of coexisting clinopyroxene. Marked geochemical gradients occur toward apatite and carbonate-bearing domains which are randomly distributed in both the sections examined. In these regions, pyroxenes and amphibole (edenite) are lower in mg## and higher in Na₂O, and spinels and phlogopite are richer in Cr₂O₃. Both the mineral assemblage and the incompatible trace element characteristics of the mineral phases recall the typical signatures of “carbonatite” metasomatism (HFSE depletion, Sr, LILE and LREE enrichment). Clinopyroxene has higher REE and Sr concentrations than amphibole (^amph/cpxD_REE,Sr = 0.7–0.9) and lower Ti and Zr concentrations. It is proposed that the petrographic and geochemical features observed at Finero are consistent with a subduction environment. The lack of chemical gradients between pyroxenite and peridotite is explained by a model where melts derived from an eclogite-facies slab infiltrate the overhanging harzburgitic mantle wedge and, because of the special thermal structure of subduction zones, become heated to the temperature of the peridotite. If the resulting temperature is above that of the incipient melting of the hydrous peridotite system, the slab-derived melt equilibrates with the harzburgite and a crystal mush consisting of harzburgite and a silica saturated, hydrous melt is formed. During cooling, the crystal mush crystallizes producing the observed sequence of mineral phases and their observed chemical characteristics. In this context pyroxenites are regions of higher concentration of the melt in equilibrium with the harzburgite and not passage-ways through which exotic melts percolated. Only negligible chemical gradients can appear as an effect of the crystallization process, which also accounts for the high amphibole/clinopyroxene incompatible trace element ratios. The major element refractory composition is explained by an initially high peridotite/melt ratio. The apatite, carbonate-bearing domains are the result of the presence of some CO₂ in the slab-derived melt. The CO₂/H₂O ratio in the peridotite mush increased by crystallization of hydrous phases (amphibole and phlogopite) locally resulting in the unmixing of a late carbonate fluid. The proposed scenario is consistent with subduction of probably Variscan age and with the occurrence of modal metasomatism before peridotite incorporation in the crust. Received: 20 July 1998 / Accepted: 28 October 1998     

Carbonate assimilation in magmas: A reappraisal based on experimental petrology

The main effect of magma–carbonate interaction on magma differentiation is the formation of a silica-undersaturated, alkali-rich residual melt. Such a desilication process was explained as the progressive dissolution of CaCO₃ in melt by consumption of SiO₂ and MgO to form diopside sensu stricto. Magma chambers emplaced in carbonate substrata, however, are generally associated with magmatic skarns containing clinopyroxene with a high Ca-Tschermak activity in their paragenesis. Data are presented from magma–carbonate interaction experiments, demonstrating that carbonate assimilation is a complex process involving more components than so far assumed. Experimental results show that, during carbonate assimilation, a diopside–hedenbergite–Ca-Tschermak clinopyroxene solid solution is formed and that Ca-Tschermak/diopside and hedenbergite/diopside ratios increase as a function of the progressive carbonate assimilation. Accordingly, carbonate assimilation reaction should be written as follows, taking into account all the involved magmatic components:CaCO₃^solid + SiO₂^melt + MgO^melt + FeO^melt + Al₂O₃^melt → (Di–Hd–CaTs)_ss^solid + CO₂^fluidThe texture of experimental products demonstrates that carbonate assimilation produces three-phases (solid, melt, and fluid) whose main products are: i) diopside–hedenbergite–Ca-Tschermak clinopyroxene solid solution; ii) silica-undersaturated CaO-rich melt; and iii) C–O–H fluid phase. The silica undersaturation of the melt and, more importantly, the occurrence of a CO₂-rich fluid phase, must be taken into account as they significantly affect partition coefficients and the redox state of carbonated systems, respectively.     

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

Summary We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes “fassaitic” clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (T_HOM = 1000–1050 °C), b) CO₂ ± H₂S-rich fluid inclusions (T_HOM = 20–31.3 °C into the vapor phase), c) multiphase aqueous brine inclusions (T_HOM = 720–820 °C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (T_HOM = 870–890 °C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt – aqueous chloride-rich liquid – carbonate/sulfate melt?) during heating and cooling below 870 °C. There is no evidence for fluid circulation below 700 °C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable ²⁰⁶Pb/²⁰⁴Pb (19.047–19.202), ²⁰⁷Pb/²⁰⁴Pb (15.655–15.670), and ²⁰⁸Pb/²⁰⁴Pb (38.915–39.069) and relatively low ¹⁴³Nd/¹⁴⁴Nd (0.51211–0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (δ¹³C_V-PDB = −5.4 to −1.1‰; δ18O_V-SMOW = 11.7 to 16.4‰) indicate formation from a ¹⁸O- and ¹³C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO₂-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns. Received March 1, 2000; revised version accepted November 2, 2000     

Effect of water on tholeiitic basalt phase equilibria: an experimental study under oxidizing conditions

To investigate the effect of water on phase relations and compositions in a basaltic system, we performed crystallization experiments at pressures of 100, 200 and 500 MPa in a temperature range of 940 to 1,220°C using four different water contents. Depending on the water activity, the oxygen fugacity varied between 1 and 4 log units above the quartz-magnetite-fayalite buffer. Addition of water to the dry system shifts the solidus > 250°C to lower temperatures and increases the amount of melt drastically. For instance, at 1,100°C and 200 MPa, the melt fraction increases from 12.5 wt% at a water content of 1.6 wt% to 96.3% at a water content of 5 wt% in the melt. The compositions of the experimental phases also show a strong effect of water. Plagioclase is shifted to higher anorthite contents by the addition of water. Olivine and clinopyroxene show generally higher MgO/FeO ratios with added water, which could also be related to the increasing oxygen fugacity with water. Moreover, water affects the partitioning of certain elements between minerals and melts, e.g., the Ca partitioning between olivine and melt. Plagioclase shows a characteristic change in the order of crystallization with water that may help to explain the formation of wehrlites intruding the lower oceanic crust (e.g., in Oman, Macquarie Island). At 100 MPa, plagioclase crystallizes before clinopyroxene at all water contents. At pressures > 100 MPa, plagioclase crystallizes before clinopyroxene at low water contents (e.g. < 3 wt%), but after clinopyroxene at H₂O in the melt > 3 wt%. This change in crystallization order indicates that a paragenesis typical for wehrlites (olivine–clinopyroxene–without plagioclase) is stabilized at low pressures typical of the oceanic crust only at high water contents. This opens the possibility that typical wehrlites in the oceanic crust can be formed by the fractionation and accumulation of olivine and clinopyroxene at 1,060°C and > 100 MPa in a primitive tholeiitic basaltic system containing more than 3 wt% water. The comparison of the experimental results with evolution trends calculated by the thermodynamic models “MELTS” and “Comagmat” shows that neither model predicts the experimental phase relations with sufficient accuracy.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Platinum-group minerals from placers related to the Nizhni Tagil (Middle Urals, Russia) Uralian-Alaskan-type ultramafic complex: ore-mineralogy and study of silicate inclusions in (Pt, Fe) alloys

Summary The study of platinum-group minerals (PGM) concentrates from the Nizhni Tagil placers related to the Soloviev Mountain (Gora Solovieva) Uralian-Alaskan-type intrusion revealed a predominance of (Pt, Fe) alloys over Ir-, and Os-bearing alloys. (Pt, Fe) alloys (“isoferroplatinum-type”) are interstitial with respect to chromite and show important variations in their chemical compositions, which are, however, falling within the experimentally determined stability field of isoferroplatinum. Tetraferroplatinum, enriched in Cu and Ni and tulameenite represent low-temperature mineral phases replacing (Pt, Fe) alloys. Alloys belonging to the Os–Ir–Ru ternary system have compositions corresponding to native osmium, iridium and ruthenium, respectively, and to rutheniridosmine. Osmium exsolutions appear in Ir-, and (Pt, Fe) alloys, and iridium exsolutions in (Pt, Fe) alloys. Laurite is a high-temperature phase included in native iridium and (Pt, Fe) alloys. Low-temperature PGM association comprises Ir-bearing sulpharsenides, including a phase (Ir, Os, Fe, Pt, Ru, Ni)₃(As, Sb)_0.85S, and a palladium antimonide Pd₂₀Sb₇. These two phases were previously unknown in nature. Furthermore, native palladium occurs in the studied concentrates. This low-temperature paragenesis indicates an interaction of Pt-, Os-, Ir- and Ru-bearing alloys with late fluids enriched in volatiles, As and Sb. The chromite composition is characterized by the predominance of Cr³⁺ → Fe³⁺ substitution like in other Uralian-Alaskan-type intrusions; that indicates a fO₂ variation during the chromite precipitation. Monomineralic inclusions of euhedral clinopyroxene and chromite crystals in (Pt, Fe) alloys were observed. Furthermore, (Pt, Fe) alloys contain polyphase silicate inclusions, which occupy the alloy negative crystals. Two types of silicate inclusions were recognized: (1) Low-pressure inclusions composed of amphibole, biotite, Jd-poor clinopyroxene, magnetite, apatite and glass; (2) High-pressure inclusions include: omphacitic clinopyroxene (up to 56 mol.% Jd), tremolite, muscovite, apatite, titanite and glass. In this case, the clinopyroxene is strongly zoned, revealing a pressure drop from about 25 to 5 kbar. The chemical composition of glass is corundum-normative and its H₂O content varies from about 12 to 15 wt.%. The composition of magmatic melts, from which the silicate inclusions have originated was estimated using EPMA and image analysis interpreted by stereology. Their compositions are close to those obtained experimentally by hydrous partial melting of upper mantle rocks. The interpretation of analytical data shows that magmatic melts entrapped by (Pt, Fe) alloys crystallized from about 1100 to 700 °C. The (Pt, Fe) alloys formed after the crystallization of chromite, clinopyroxene and albite. Consequently, the precipitation temperature of (Pt, Fe) alloys is estimated at about 900 °C. The significant pressure drop implies a decrease of volatile concentrations in the magmatic melt and the possible formation of a fluid phase, which might have generated, the precipitation of chromite and PGM.     

Dolomite-bearing orogenic garnet peridotites witness fluid-mediated carbon recycling in a mantle wedge (Ulten Zone,Eastern Alps,Italy)

We document the presence of dolomite ± apatite in orogenic peridotites from the Ulten Zone (UZ, Italian Alps), the remnants of a Variscan mantle wedge tectonically coupled with eclogitized continental crust. These dolomite peridotites are associated with dominant carbonate-free amphibole peridotites, which formed in response to infiltration of aqueous subduction fluids lost by the associated crustal rocks during high-pressure (HP) metamorphism and retrogression. Dolomite-free and dolomite-bearing peridotites share the same metamorphic evolution, from garnet- (HP) to spinel-facies (low-pressure, LP) conditions. Dolomite and the texturally coexisting phases display equilibrium redistribution of rare earth elements and of incompatible trace elements during HP and LP metamorphism; clinopyroxene and amphiboles from carbonate-free and carbonate-bearing peridotites have quite similar compositions. These features indicate that the UZ mantle rocks equilibrated with the same metasomatic agents: aqueous CO₂-bearing fluids enriched in incompatible elements released by the crust. The P–T crystallization conditions of the dolomite peridotites (outside the field of carbonatite melt + amphibole peridotite coexistence), a lack of textures indicating quench of carbonic melts, a lack of increase in modal clinopyroxene by reaction with such melts and the observed amphibole increase at the expense of clinopyroxene, all suggest that dolomite formation was assisted by aqueous CO₂-bearing fluids. A comparison of the trace element compositions of carbonates and amphiboles from the UZ peridotites and from peridotites metasomatized by carbonatite and/or carbon-bearing silicate melts does not help to unambiguously discriminate between the different agents (fluids or melts). The few observed differences (lower trace element contents in the fluid-related dolomite) may ultimately depend on the solute content of the metasomatic agent (CO₂-bearing fluid versus carbonatite melt). This study provides strong evidence that C–O–H subduction fluids can produce ‘carbonatite-like’ assemblages in mantle rocks, thus being effective C carriers from the slab to the mantle wedge at relatively low P–T. If transported beyond the carbonate and amphibole solidus by further subduction, dolomite-bearing garnet + amphibole peridotites like the ones from Ulten can become sources of carbonatite and/or C-bearing silicate melts in the mantle wedge. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. In memory of Lauro Morten 1941–2006.     

Petrology of ultramafic lamprophyres from the Beaver Lake area of Eastern Antarctica and their relation to the breakup of Gondwanaland

Summary Mesozoic melilite-bearing ultramafic lamprophyres are developed as sill, dyke and plug-like intrusive bodies in the East Antarctic Beaver Lake area. They consist of varying amounts of olivine, melilite, phlogopite, nepheline, titanomagnetite and perovskite as major phases, accompanied by minor amounts of apatite, carbonate, spinel, glass and, rarely, monticellite. The rocks are mineralogically and geochemically broadly similar to olivine melilitites, differing in higher CO₂ and modal phlogopite and carbonate contents. The ultramafic lamprophyres are MgO-rich (13.4–20.5 wt%) and SiO₂-poor (32.8–37.2 wt%), indicative of a near-primary nature. Major and trace element features are consistent with minor fractionation of olivine and Cr-spinel from melts originating at depths of 130–140 km. Primary melts originated by melting of upper mantle peridotite which had been veined by phlogopite + carbonate + clinopyroxene-bearing assemblages less than 200 Ma before eruption. The presence of the veins and their time of formation is required to explain high incompatible trace element contents and growth of ⁸⁷Sr/⁸⁶Sr, leaving ¹⁴³Nd/¹⁴⁴Nd unaffected. The major element, compatible trace element, and most radiogenic isotope characteristics are derived from melting of the wall-rock peridotite. The depth of about 130 km is indicated by the presence of phlogopite rather than amphibole in the veins, by control of the REE pattern by residual garnet, by the high MgO content of the rocks, and by the expected intersection of the rift-flank geotherm with the solidus at this depth. The higher CO₂ contents than are characteristic for olivine melilitites favoured the crystallization of melilite at crustal pressures, and suppressed the crystallization of clinopyroxene. The Beaver Lake ultramafic lamprophyres are a distal effect of the breakup of Gondwanaland, too distal to show a geochemical signature of the Kerguelen plume. Upward and outward movement of the asthenosphere-lithosphere boundary beneath the Lambert-Amery rift led first to the production of phlogopite- and carbonate-rich veins, and later to the generation of the ultramafic lamprophyres themselves. Received March 31, 2000; revised version accepted September 3, 2001     

Experimental constraints on the origin and evolution of mildly alkalic basalts from the Kerguelen Archipelago, Southeast Indian Ocean

This experimental study examines the role of clinopyroxene fractionation on major element trends and alkalinity variations in mildly alkalic basalts from the Kerguelen Archipelago, Southeast Indian Ocean. Equilibrium crystallization experiments were carried out on a natural basalt (MgO=5 wt.%, alkalinity index=0.10) over a range of pressures (0–1.43 GPa) and water contents (nominally dry to hydrous, 1.2 wt.% H₂O) under relatively oxidizing conditions (Δlog FMQ=+1 to +2) at 0 GPa and relatively reducing conditions (Δlog FMQ=0 to –2) at all higher pressures. The hydrous experiments at 0.93 GPa closely reproduce most of the compositional variations in the 24–25 Ma mildly alkalic lavas from the archipelago, which supports a major role for high-Al clinopyroxene fractionation (5–9 wt.% Al₂O₃) at pressures corresponding to the base of the Northern Kerguelen Plateau (15–20 km). However, clinopyroxene fractionation at depth fails to produce important changes in the alkalinity of the residual melts. The transition from tholeiitic to mildly alkalic basalts on the Kerguelen Archipelago thus reflects primarily changes in melting conditions (lower extents of partial melting at higher pressures), which is related to crustal and lithospheric thickening as distance from the Southeast Indian Ridge increased over time from 43 to 24 Ma.     

Pervasive assimilation of carbonate and silicate rocks in the Hortavær igneous complex, north-central Norway

The intrusive complex at Hortavær represents a magma transfer zone in which multiple pulses of gabbroic and dioritic magmas evolved along Fe- and alkali-enrichment trends. Extreme alkali enrichment resulted in nepheline-normative and sparse nepheline-bearing monzodioritic and monzonitic rocks. More evolved monzonitic and syenitic rocks are silica saturated and, in some cases, quartz bearing. Previous and current research recognized an abundance of clinopyroxene and other Ca-rich phases, such as scapolite, grossular-rich garnet, and igneous-textured calcite among the mafic and intermediate rocks. Even the most pyroxene-rich samples contain low Sc concentrations, which suggests early, intense fractionation of clinopyroxene. These features and the alkali enrichment are consistent with assimilation of carbonate-rich host rocks. Carbon isotope ratios of the igneous-textured calcite indicate an origin of the carbon from host rocks rich in calcite, consistent with assimilation. However, low _Nd values (−3.4 to −10.2) and moderate initial ⁸⁷Sr/⁸⁶Sr values (0.7052 to 0.7099) indicate the need for assimilation of quartzofeldspathic rocks as well. Models of combined assimilation and fractional crystallization indicate that assimilation of simple end members, either carbonate or silicate, cannot explain the entire data set. Instead, variable proportions of carbonate and silicate materials were assimilated, with the most pronounced assimilation effects in the mafic rocks. The reasons for variable degrees of assimilation are, as yet, uncertain. It is possible that assimilation of calc-silicate rocks with variable carbonate/silicate proportions resulted in the range of observed compositions. However, the importance of carbonate assimilation in mafic rocks compared to felsic ones suggests that assimilation of carbonates was predominant at high temperature and/or mafic magma compositions and assimilation of silicates was predominant at lower temperature and/or felsic magma compositions. We suggest that the ability of the mafic magma to dissolve higher proportions of carbonate contaminants is the result of the magma's ability to form clinopyroxene as a product of assimilation. In any case, extensive carbonate assimilation was possible because CO₂ escaped from the system.     

Recycled crustal melt injection into lithospheric mantle: implication from cumulative composite and pyroxenite xenoliths

A rare composite xenolith and abundant cumulative pyroxenites obtained from the Mesozoic Fangcheng basalts on the eastern North China Craton record a complex history of melt percolation and circulation in the subcontinental lithospheric mantle. The composite xenolith has a dunite core and an olivine clinopyroxenite rim. The dunite is of cumulative origin and has a granular recrystallized texture and extremely low Mg# [100 Mg/(Mg + Fe) = 81–82] contents in olivines. The olivine clinopyroxenite contains larger clinopyroxene and/or orthopyroxene with a few fine-grained olivine and tiny phlogopite, feldspar, and/or carbonate minerals interstitial to clinopyroxene. The clinopyroxene has low Mg# (83–85). Compositional similarity between dunitic olivine and pyroxenitic one indicates a sequential crystallization of dunite and pyroxenite from a precursor melt. Pyroxenite xenoliths include olivine websterites and clinopyroxenites, both are of cumulative origin. Estimation of the melt from major oxides in olivines and REE concentrations in clinopyroxenes in these composite and pyroxenite xenoliths suggests a derivation from subducted crustal materials, consistent with the highly enriched EMII-like Sr and Nd isotopic ratios observed in the pyroxenites. Occurrence of phlogopite, feldspar and carbonate minerals in some xenoliths requires the melt rich in alkalis (K, Na), silica and volatiles (water and CO₂) at the latest stage as well, similar to highly silicic and potassic melts. Thus, the occurrence of these composite and pyroxenite xenoliths provides an evidence for voluminous injection of recycled crustal melts into the lithosphere beneath the southeastern North China Craton at the Late Mesozoic, a reason for the rapid lithospheric enrichment in both elemental and isotopic compositions.     

Early Cambrian oceanic plagiogranite in the Silvretta Nappe,eastern Alps: geochemical,zircon U-Pb and Rb-Sr data from garnet-hornblende-plagioclase gneisses

 Garnet–hornblende–plagioclase gneisses rich in incompatible elements occur in the crystalline basement of the Austro-Alpine Silvretta nappe and are associated with clinopyroxene norites and harzburgite cumulates. It is proposed here that the gneisses were formerly oceanic plagiogranites. An ε_{Nd( 530 )} value of +5.6 for the gneisses as well as initial ⁸⁷Sr/⁸⁶Sr values of 0.7036–0.7037 for the gabbroic rocks and 0.7026–0.7027 for the ultramafic rocks suggest a mantle source for this rock association. The geochemical characteristics of the garnet–hornblende–plagioclase gneisses indicate that their precursors were derived by fractional crystallization from a basaltic parent magma, by the same process which produced the adjacent clinopyroxene norites and ultramafic cumulates as well. The combined U–Pb upper intercept ages of zircons from two gneiss samples yield an igneous crystallization age of 532±30 Ma, similar to previously dated (mostly calc-alkaline) orthogneisses in the same area. High-quality transparent zircons showed the least degree of discordance, but contain extremely low U and Pb levels. The rock suite, including this plagiogranite, was emplaced within oceanic crust which formed in the latest Precambrian–early Palaeozoic off the northern continental margin of Gondwana. Received: 26 April 1996 / Accepted: 2 August 1996     

Platinum-group minerals from the Jinbaoshan Pd–Pt deposit,SW China: evidence for magmatic origin and hydrothermal alteration

The Jinbaoshan Pt–Pd deposit in Yunnan, SW China, is hosted in a wehrlite body, which is a member of the Permian (∼260 Ma) Emeishan Large Igneous Province (ELIP). The deposit is reported to contain one million tonnes of Pt–Pd ore grading 0.21% Ni and 0.16% Cu with 3.0 g/t (Pd + Pt). Platinum-group minerals (PGM) mostly are ∼10 μm in diameter, and are commonly Te-, Sn- and As-bearing, including moncheite (PtTe₂), atokite (Pd₃Sn), kotulskite (PdTe), sperrylite (PtAs₂), irarsite (IrAsS), cooperite (PtS), sudburyite (PdSb), and Pt–Fe alloy. Primary rock-forming minerals are olivine and clinopyroxene, with clinopyroxene forming anhedral poikilitic crystals surrounding olivine. Primary chromite occurs either as euhedral grains enclosed within olivine or as an interstitial phase to the olivine. However, the intrusion has undergone extensive hydrothermal alteration. Most olivine grains have been altered to serpentine, and interstitial clinopyroxene is often altered to actinolite/tremolite and locally biotite. Interstitial chromite grains are either partially or totally replaced by secondary magnetite. Base-metal sulfides (BMS), such as pentlandite and chalcopyrite, are usually interstitial to the altered olivine. PGM are located with the BMS and are therefore also interstitial to the serpentinized olivine grains, occurring within altered interstitial clinopyroxene and chromite, or along the edges of these minerals, which predominantly altered to actinolite/tremolite, serpentine and magnetite. Hydrothermal fluids were responsible for the release of the platinum-group elements (PGE) from the BMS to precipitate the PGM at low temperature during pervasive alteration. A sequence of alteration of the PGM has been recognized. Initially moncheite and atokite have been corroded and recrystallized during the formation of actinolite/tremolite, and then, cooperite and moncheite were altered to Pt–Fe alloy where they are in contact with serpentine. Sudburyite occurs in veins indicating late Pd mobility. However, textural evidence shows that the PGM are still in close proximity to the BMS. They occur in PGE-rich layers located at specific igneous horizons in the intrusion, suggesting that PGE were originally magmatic concentrations that, within a PGE-rich horizon, crystallized with BMS late in the olivine/clinopyroxene crystallization sequence and have not been significantly transported during serpentinization and alteration.     

Melting experiments on the enstatite-diopside join at 70–224 kbar,including the melting of diopside

 Melting relations on the enstatite−diopside (En, Mg₂Si₂O₆−Di, CaMgSi₂O₆) join, including the compositions of crystalline phases and melts coexisting along the solidi, were experimentally determined in the pressure range 70–224 kbar with a split-sphere anvil apparatus (USSA-2000). Melting is peritectic in enstatite-rich compositions at 70–124 kbar (1840–2100° C) and eutectic at higher pressures, while the diopside-rich clinopyroxene melts azeotropically at 70–165 kbar and up to 300° C lower temperatures than the eutectic. Orthopyroxene is replaced with enstatite-rich clinopyroxene at 120 kbar and 2090°C. First garnet with 17 mol% Di forms on the solidus at 158 kbar and 2100° C. Two garnets coexist on the solidus at 165–183 kbar and 2100° C, garnet coexists with CaSiO₃ perovskite at 183–224 kbar (2100–2230° C) and two coexisting perovskites are stable at higher pressures. The melting curve of diopside was determined at 80–170 kbar; the slope becomes negative at 140 kbar and 2155° C. At 170 kbar and 2100° C, diopside with 96% Di breaks down to garnet with 89% Di and CaSiO₃ perovskite. The new data were used to calculate an improved temperature-pressure phase diagram for the CMAS system, which can be useful for estimating the mineralogy of the Earth's upper mantle. Received: 15 October 1994 / Accepted: 15 October 1995     

C2/c pyroxene phenocrysts from three potassic series in the Neogene alkaline volcanics, NE Turkey: their crystal chemistry with petrogenetic significance as an indicator of P–T conditions

Chemical and structural data are reported for C2/c pyroxene phenocrysts collected from three potassic series (Group A: basanite-tephrite, Group B: tephrite-phonolitic tephrite, Group C: alkaline basalt-trachybasalt) of the Neogene alkaline volcanics (NAVs) in northeastern Turkey, in order to investigate the evolution of the magmatic plumbing system and the location of magma chamber(s) with crystallization conditions. The rock series hosting the clinopyroxene phenocrysts show generally porphyritic texture and have a variable phenocryst-rich nature (20–58%), with phenocryst assemblages characterized by cpx ± ol ± plag ± foid ± amp ± bio. The clinopyroxene phenocrysts can be chemically classified as Ti- and Fe³⁺-rich Al-diopsides for Groups A and B (AB-cpxs) and Ti- and Fe³⁺-poor Al-diopsides for Group C (C-cpxs). They have poorly variable composition, clustering in the diopside field. Structurally, the diopside groups have nearly similar a (ranging from 9.73 to 9.75 ?), V _cell (437.2–440.9 ?³), and 〈beta〉 angle values (106.01°–106.23°), but some differences in polyhedral parameters and geometries of the AB-cpxs and C-cpxs have been observed. For example, the AB-cpxs are characterized by larger c (5.27–5.30 vs. 5.25–5.28 ?), V _T (2.27–2.30 vs. 2.23–2.28 ?³), and V _M2 (25.53–25.72 vs. 25.41–25.59 ?³) values and smaller b (8.87–8.88 vs. 8.88–8.91 ?) and V _M1 (11.49–11.63 vs. 11.64–11.83 ?³) values with respect to the C-cpxs. In addition, the AB-cpxs show higher values of V _M2/V _M1 (2.20–2.23) due to large V _M2 and small V _M1 compared to the V _M2/V _M1 ratios of the C-cpxs (<2.19). Such differences in the crystal structure of the AB-cpxs and C-cpxs from the NAVs are partly related to different crystallization pressures, but mostly related to variation in melt composition and, possibly, the influence of other crystallizing mineral phases. In particular, R(M2-O1) and R(M1-O2) (i.e. bond lengths) differences in the clinopyroxenes of different groups support the presence of evolved host rocks with different alkaline character (i.e. silica-undersaturated Groups A–B and silica-saturated Group C). Based on the cpx-geothermobarometry, the crystallization pressures for the C-cpxs are lower than 4.5 kbars, but the AB-cpxs have relatively high-pressure values (5.6–10.6 kbars), suggesting that the AB-cpxs crystallized in higher pressure environments. The relatively higher crystallization temperatures of the AB-cpxs also indicate higher cooling rates. The P–T estimates suggest that the source regions of the clinopyroxene phenocrysts from the NAVs were crustal magma chambers in a closed plumbing system at a moderate- to low-pressure regime.     

Abundant Fe–Ti oxide inclusions in olivine from the Panzhihua and Hongge layered intrusions, SW China: evidence for early saturation of Fe–Ti oxides in ferrobasaltic magma

Abundant Fe–Ti oxide inclusions in cumulus olivine (Fo_77–81) from the Panzhihua and Hongge intrusions, Emeishan large igneous province, SW China, document the first evidence for early crystallization of Fe–Ti oxides in ferrobasaltic systems in nature. The intrusions also contain significant stratiform Fe–Ti–V oxide ores. The oxide inclusions are sub-rounded or irregular, range from ∼5 to 50 μm in diameter, and are dominated by either titanomagnetite or ilmenite. The fact that the inclusions are either titanomagnetite- or ilmenite-dominant suggests that they are trapped crystals, instead of immiscible oxide melt, formed during growth of the host olivine. The absence of other silicate phases in the inclusion-bearing olivine is difficult to reconcile with a possible xenocrystic origin of the oxide inclusions. These oxide inclusions are thus interpreted to be cumulus minerals crystallized together and trapped in olivine from the same parental magma. In addition to Fe–Ti oxides, some inclusions contain amphibole + biotite ± fluorapatite that might have formed by reaction of trapped hydrous liquid with the host olivine. Numerical modeling of high-Ti Emeishan basalts using the MELTS program successfully simulates early crystallization of olivine (∼Fo₈₁) and Fe–Ti spinel in the presence of a moderate amount of H₂O (∼1.5 wt%) under pressure and fO₂ conditions generally pertinent to the Panzhihua and Hongge intrusions. The modal mineralogy of the oxide inclusions is in good agreement with the bulk compositions of the ore, as inferred from whole-rock data, in a given intrusion. This is consistent with the interpretation that the stratiform oxide ores in the intrusions formed by accumulation of Fe–Ti oxide crystals that appeared on the liquidus with olivine and clinopyroxene.     

Petrogenesis of the amphibole-rich veins from the Lherz orogenic lherzolite massif (Eastern Pyrenees, France): a case study for the origin of orthopyroxene-bearing amphibole pyroxenites in the lithospheric mantle

The Lherz orogenic lherzolite massif (Eastern French Pyrenees) displays one of the best exposures of subcontinental lithospheric mantle containing veins of amphibole pyroxenites and hornblendites. A reappraisal of the petrogenesis of these rocks has been attempted from a comprehensive study of their mutual structural relationships, their petrography and their mineral compositions. Amphibole pyroxenites comprise clinopyroxene, orthopyroxene and spinel as early cumulus phases, with garnet and late-magmatic K₂O-poor pargasite replacing clinopyroxene, and subsolidus exsolution products (olivine, spinel II, garnet II, plagioclase). The original magmatic mineralogy and rock compositions were partly obscured by late-intrusive hornblendites and over a few centimetres by vein–wallrock exchange reactions which continued down to subsolidus temperatures for Mg–Fe. Thermobarometric data and liquidus parageneses indicate that amphibole pyroxenites started to crystallize at P ≥ 13 kbar and recrystallized at P < 12 kbar. The high Al^VI/Al^IV ratio (>1) of clinopyroxenes, the early precipitation of orthopyroxene and the late-magmatic amphibole are arguments for parental melts richer in silica but poorer in water than alkali basalts. Their modelled major element compositions are similar to transitional alkali basalt with about 1–3 wt% H₂O. In contrast to amphibole pyroxenites, hornblendites only show kaersutite as liquidus phase, and phlogopite as intercumulus phase. They are interpreted as crystalline segregates from primary basanitic magmas (mg=0.6; 4–6 wt% H₂O). These latter cannot be related to the parental liquids of amphibole pyroxenites by a fractional crystallization process. Rather, basanitic liquids mostly reused pre-existing pyroxenite vein conduits at a higher structural level (P ≤ 10 kbar). A continuous process of redox melting and/or alkali melt/peridotite interaction in a veined lithospheric mantle is proposed to account for the origin of the Lherz hydrous veins. The transitional basalt composition is interpreted in terms of extensive dissolution of olivine and orthopyroxene from wallrock peridotite by alkaline melts produced at the mechanical boundary layer/thermal boundary layer transition (about 45–50 km deep). Continuous fluid ingress allowed remelting of the deeper veined mantle to produce the basanitic, strongly volatiles enriched, melts that precipitated hornblendites. A similar model could be valid for the few orthopyroxene-rich hydrous pyroxenites described in basalt-hosted mantle xenoliths. Received: 15 September 1999 / Accepted: 31 January 2000     

Experimental constraints on the effects of pressure and H2O on the fractional crystallization of high-Mg island arc basalt

H₂O-undersaturated melting experiments of synthesized basalt (SiO₂ = 50.7 wt.%, MgO = 8.3 wt.%, Mg# = 60) were conducted at fO₂ corresponding to NNO+1 and NNO−1 to clarify the effects of pressure (2–7 kbar) and H₂O on fractional crystallization in island arcs. H₂O content was ranged from nominally anhydrous to 4.4 wt.%. Differentiation trends, namely the liquid lines of descent, change sensitively according to pressure-H₂O relations. Tholeiitic differentiation trends are reproduced with H₂O ≤ ∼2 wt.% in primary magma. With such quantities of H₂O, fractional crystallization is controlled by olivine + plagioclase at 2 kbar. Increasing the pressure from 2 to ≥4 kbar induces early crystallization of orthopyroxene instead of olivine and therefore SiO₂ enrichment in the residual melts is suppressed. Increasing H₂O (≥ ∼2 wt.% in primary magma) stabilizes clinopyroxene relative to orthopyroxene and/or magnetite. Although the phase relations and proportions strongly depend on fO₂ and H₂O content, differentiation trends are always calc-alkaline.     

Crystallization of primitive basaltic magmas at crustal pressures and genesis of the calc-alkaline igneous suite: experimental evidence from St Vincent,Lesser Antilles arc

Near-liquidus crystallization experiments have been carried out on two basalts (12.5 and 7.8 wt% MgO) from Soufriere, St Vincent (Lesser Antilles arc) to document the early stages of differentiation in calc-alkaline magmas. The water-undersaturated experiments were performed mostly at 4 kbar, with 1.6 to 7.7 wt% H₂O in the melt, and under oxidizing conditions (ΔNNO = −0.8 to +2.4). A few 10 kbar experiments were also performed. Early differentiation of primitive, hydrous, high-magnesia basalts (HMB) is controlled by ol + cpx + sp fractionation. Residual melts of typical high-alumina basalt (HAB) composition are obtained after 30–40% crystallization. The role of H₂O in depressing plagioclase crystallization leads to a direct relation between the Al₂O₃ content of the residual melt and its H₂O concentration, calibrated as a geohygrometer. The most primitive phenocryst assemblage in the Soufriere suite (Fo_89.6 olivine, Mg-, Al- and Ti-rich clinopyroxene, Cr–Al spinel) crystallized from near-primary (Mg# = 73.5), hydrous (∼5 wt% H₂O) and very oxidized (ΔNNO = +1.5–2.0) HMB liquids at middle crustal pressures and temperatures from ∼1,160 to ∼1,060°C. Hornblende played no role in the early petrogenetic evolution. Derivative HAB melts may contain up to 7–8 wt% dissolved H₂O. Primitive basaltic liquids at Soufriere, St Vincent, have a wide range of H₂O concentrations (2–5 wt%).