Lead isotope variability in olivine-hosted melt inclusions from Iceland

The lead isotope and trace element compositions of a suite of olivine-hosted melt inclusions in primitive lava flows from the Reykjanes Peninsula in Iceland show extreme variability. Much of this variability is present in the composition of inclusions from one hand specimen of Háleyjabunga, a depleted picrite lava shield that erupted 13 ka. ²⁰⁸Pb/²⁰⁶Pb compositions in this sample span 50-90% of the total range found in Atlantic MORB, indicating that high-amplitude compositional heterogeneity is present in the mantle source of melts that aggregated to form a single eruption. The trace element and isotopic trends in the melt inclusions are coincident with those in whole rock samples from young lava flows of the Reykjanes Peninsula, and extend the total range of variation towards more depleted compositions. The incompatible trace element and lead isotope compositions of the inclusions are strongly coupled and lie close to binary mixing trends between the extreme melt inclusion compositions. These relationships indicate that the trace element variation in the melt inclusions reflects heterogeneity in the composition of the mantle source entering the melting region under the Reykjanes Peninsula. Large positive Sr concentration anomalies are present in three of the inclusions, but do not correlate with indicators of mantle melting or source variations and are likely to arise by reaction with plagioclase during crustal storage. Fractional melting of heterogeneous mantle is predicted to generate melts with a wide range of compositions, filling a large volume in trace element-isotope space. However, the compositional variations observed in the melt inclusions lie close to binary mixing curves. These observations may be accounted for by a two-stage model of melt mixing. The first stage occurs in porous channels that transport melt in the mantle and takes place before inclusion entrapment. This mixing stage generates a bimodal distribution of melt compositions that is supplied from the channels to sub-Moho and lower crustal magma lenses. The second stage of mixing occurs in these chambers, producing the binary mixing trends recorded in the inclusion compositions. The distribution of isotopic compositions observed in the melt inclusions and whole rock samples from the Reykjanes Peninsula is therefore controlled by melt mixing. These results have important implications for the interpretation of basalt composition in terms of distinct compositional entities within the upwelling solid mantle under mid-ocean ridges and ocean islands.     

Evacuation of multiple magma bodies and the onset of caldera collapse in a supereruption,captured in glass and mineral compositions

Complexities in the nature of large-scale silicic eruptions and their magmatic systems can be discerned through micro-analytical geochemical studies. We present high-resolution, stratigraphically constrained compositional data on glassy matrix material and feldspar crystals from the initial fall deposits and earliest ignimbrite (base of member A) of the 2.08 Ma, ~?2500 km³ Huckleberry Ridge Tuff (HRT), Yellowstone. We use these data to document the nature of the magmatic system and compositional changes related to the transition from fall to widespread ignimbrite deposition, inferred to mark the onset of caldera collapse. Although major element glass compositions are relatively uniform, trace elements span a large range (e.g. Ba 10–900 ppm, Sr/Rb?=?0.005–0.09), with highly evolved glasses dominating in the fall deposits. Several trace elements (e.g. Ba and light rare earth elements) in the glass samples serve to define statistically significant compositional clustering in the fall deposits and basal ignimbrite. These clusters are inferred to reflect melt compositions controlled by fractional crystallisation processes and are interpreted to represent multiple, discrete melt-dominant domains that were tapped by multiple vents. The onset of widespread ignimbrite deposition is marked by an increase in the number of erupted melt compositional clusters from four in the fall deposits to eight, representing nine melt-dominant domains. There is an absence of geographical variation of glass compositions within the basal ignimbrite, with samples from proximal to distal localities north, west and south of the HRT caldera exhibiting similar variability. Pairing of glass analyses with sanidine major and minor element compositional data suggests that the nine melt compositional domains converged at depth into two compositionally distinct upper-crustal magmatic lineages that were both active during these early stages of the eruption. Our data collectively indicate the evacuation of an exceptionally complex and heterogeneous magma system. The onset of widespread ignimbrite deposition, inferred to relate to caldera collapse, occurred after ~ 50 km³ of magma had been discharged. Although external controls were important as an eruption trigger, depressurisation of the system led to caldera collapse with the eruption of numerous discrete melt-dominant domains.     

Glasses in the D'Orbigny angrite

The angrites are a small and heterogeneous group of achondritic meteorites with highly unusual chemical and mineralogical features. The abundant presence of glasses in D'Orbigny makes this rock a unique member of the angrite group. Glasses fill open spaces, form pockets, and occur as inclusions in olivines. Their physical settings exclude an incorporation from an external source. Major and trace element (rare earth elements [REE], Li, B, Be, transition elements, N and C) contents of these glasses and host olivines were measured combining laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), secondary-ion mass spectrometry (SIMS), Nuclear Reaction Analysis (NRA), and EMP techniques. Based on the major element composition, glasses filling voids could represent either a melt formed by melting an angritic rock or a melt from which angrites could have crystallized. Trace element contents of these glasses strongly indicate a direct link to the D'Orbigny bulk meteorite. They are incompatible with the formation of the glasses by partial melting of a chondritic source rock or by shock melting. The refractory elements (e.g., Al, Ti, Ca) have about 10 × CI abundances with CaO/TiO₂ and FeO/MnO ratios being approximately chondritic. Trace element abundances in the glasses appear to be governed by volatility and suggest that the refractory elements in the source had chondritic relative abundances. Although the glasses (and the whole rock) lack volatile elements such as Na and K, they are rich in some moderately volatile elements such as B, V, Mn, Fe (all with close to CI abundances), and Li (about 3-5 × CI). These elements likely were added to the glass in a sub-solidus metasomatic elemental exchange event. We have identified a novel mechanism for alteration of glass and rock compositions based on an exchange of Al and Sc for Fe and other moderately volatile elements in addition to the well-known metasomatic exchange reactions (e.g., Ca-Na and Mg-Fe).Because glass inclusions in olivine were partly shielded from the metasomatic events by the host crystal, their chemical composition is believed to be closer to the original composition than that of any other glasses. The relative trace element abundances in glasses of glass inclusions in olivine and glass pockets are also unfractionated and at the 10 to 20 × CI level. These glasses are chemically similar to the common void-filling glasses but show a much wider compositional variation. Inclusion glasses demonstrate that at least olivine grew with the help of a liquid. In analogy to olivines in carbonaceous chondrites, initial formation could also have been a vapor-liquid-solid condensation process. At that time, the glass had a purely refractory composition. This composition, however, was severely altered by the metasomatic addition of large amounts of FeO and other moderately volatile elements. The presence of volatile elements such as carbon and nitrogen in glasses of glass inclusions is another feature that appears to give these glasses a link with those hosted by olivines of carbonaceous chondrites. All these features point to an origin from a vapor with relative abundances of condensable elements similar to those in the solar nebula.     

Enrichment processes at the base of the Archean lithospheric mantle: observations from trace element characteristics of pyropic garnet inclusions in diamonds

Trace element concentrations of peridotitic garnet inclusions in diamonds from two Chinese kimberlite pipes were determined using the ion microprobe. Garnet xenocrysts from the same two kimberlite pipes were also analyzed for comparison. In contrast to their extremely refractory major element compositions, all harzburgitic garnets showed enrichment in light rare earth elements (REE) relative to chondrite, resulting in sinuous REE patterns. Both normal and sinuous REE patterns were observed from the lherzolitic garnets. Concentrations of REE in garnets changed significantly from diamond to diamond and no specific correlations were observed with their major element compositions. Analyses of randomly selected two to three points within every grain of a large number of garnet inclusions by the ion microprobe demonstrated that there was no evident compositional heterogeneity, and multiple grains of one phase from a single diamond host also exhibit very similar compositions. This implies that the trace element heterogeneity within one grain or among multiple inclusions from the same diamond host, as reported from Siberian diamonds, is not a common feature for these Chinese diamonds. Concentrations of Na, Ti, and Zr tend to decrease when garnets become more refractory, but variations of Sr and Li are more complex. Compositions rich in light REE and relatively poor in high field strength elements (HFSE) of the harzburgitic garnet inclusions in diamonds are generally consistent with metasomatism by carbonatite melts. The trace element features observed from the garnet inclusions in Chinese diamonds may be caused by carbonatite melt infiltration and partial melt extraction. Spatial and temporal gradients in melt/rock ratio and temperature are the main reasons for the large variations of REE patterns and other trace element concentrations. Received: 27 April 1999 / Accepted: 1 March 2000     

济南辉长岩岩浆演化过程:来自熔体包裹体的证据

本研究首次报道了早白垩世济南辉长岩中橄榄石斑晶捕获的熔体包裹体的研究结果。济南辉长岩中橄榄石的Fo(60.3~74.6),Mn(2500~3500μg/g),Ni(70~1349μg/g),Fe/Mn比值(61.2~83.5),与源区母岩为纯的橄榄岩形成的熔体结晶出的橄榄石性质不同,可能与源区存在辉石岩的贡献有关。橄榄石中熔体包裹体主量元素具有较大的变化范围。熔体包裹体成分的标准矿物计算(CIPW)表明,MgO10%的熔体包裹体为含有霞石和橄榄石标准矿物分子的硅不饱和熔体,Mg O10%时为含石英标准矿物分子的硅饱和熔体。橄榄石中包裹有辉石和斜长石,说明岩浆演化过程应该处于开放环境。熔体包裹体的(~208Pb/~206Pb)i和(~207Pb/~206Pb)i与MgO具有良好的负相关关系,与SiO_2具有良好的正相关关系,以及熔体包裹体具有较高的SiO_2特征表明岩浆演化过程中可能有下地壳长英质组分的加入。熔体包裹体的Pb同位素落在EMI附近并向EMII延伸,其源区可能有EMI和EMII的贡献,熔体包裹体的主量元素成分说明其源区母岩可能有橄榄岩和辉石岩的贡献。     

Composition and origin of rhyolite melt intersected by drilling in the Krafla geothermal field, Iceland

The Iceland Deep Drilling Project Well 1 was designed as a 4- to 5-km-deep exploration well with the goal of intercepting supercritical hydrothermal fluids in the Krafla geothermal field, Iceland. The well unexpectedly drilled into a high-silica (76.5 % SiO₂) rhyolite melt at approximately 2.1 km. Some of the melt vesiculated while extruding into the drill hole, but most of the recovered cuttings are quenched sparsely phyric, vesicle-poor glass. The phenocryst assemblage is comprised of titanomagnetite, plagioclase, augite, and pigeonite. Compositional zoning in plagioclase and exsolution lamellae in augite and pigeonite record changing crystallization conditions as the melt migrated to its present depth of emplacement. The in situ temperature of the melt is estimated to be between 850 and 920 °C based on two-pyroxene geothermometry and modeling of the crystallization sequence. Volatile content of the glass indicated partial degassing at an in situ pressure that is above hydrostatic (~16 MPa) and below lithostatic (~55 MPa). The major element and minor element composition of the melt are consistent with an origin by partial melting of hydrothermally altered basaltic crust at depth, similar to rhyolite erupted within the Krafla Caldera. Chondrite-normalized REE concentrations show strong light REE enrichment and relative flat patterns with negative Eu anomaly. Strontium isotope values (0.70328) are consistent with mantle-derived melt, but oxygen and hydrogen isotope values are depleted (3.1 and ?118 ‰, respectively) relative to mantle values. The hydrogen isotope values overlap those of hydrothermal epidote from rocks altered by the meteoric-water-recharged Krafla geothermal system. The rhyolite melt was emplaced into and has reacted with a felsic intrusive suite that has nearly identical composition. The felsite is composed of quartz, alkali feldspar, plagioclase, titanomagnetite, and augite. Emplacement of the rhyolite magma has resulted in partial melting of the felsite, accompanied locally by partial assimilation. The interstitial melt in the felsite has similar normalized SiO₂ content as the rhyolite melt but is distinguished by higher K₂O and lower CaO and plots near the minimum melt composition in the granite system. Augite in the partially melted felsite has re-equilibrated to more calcic metamorphic compositions. Rare quenched glass fragments containing glomeroporphyritic crystals derived from the felsite show textural evidence for resorption of alkali feldspar and quartz. The glass in these fragments is enriched in SiO₂ relative to the rhyolite melt or the interstitial felsite melt, consistent with the textural evidence for quartz dissolution. The quenching of these melts by drilling fluids at in situ conditions preserves details of the melt–wall rock interaction that would not be readily observed in rocks that had completely crystallized. However, these processes may be recognizable by a combination of textural analysis and in situ analytical techniques that document compositional heterogeneity due to partial melting and local assimilation.     

Compositional effects on element partitioning between Mg-silicate perovskite and silicate melts

High-pressure melting experiments were performed at ~26 GPa and ~2,200–2,400°C on synthetic peridotite compositions with varying FeO and Al₂O₃ contents and on a synthetic CI chondrite analogue composition. Peridotite liquids show a crystallisation sequence of ferropericlase (Fp) followed down temperature by Mg-silicate perovskite (MgPv) + Fp, which contrasts a sequence of MgPv followed by MgPv + Fp observed in the chondritic composition. The difference in crystallisation sequence is a consequence of the different bulk Mg/Si ratios. MgPv/melt partition coefficients for major, minor and trace elements were determined by electron microprobe and secondary ion mass spectrometry. Partition coefficients of tri- and tetravalent elements increase with increasing Al concentration in MgPv. A lattice strain model indicates that Al³⁺ substitutes predominantly onto the Si-site in MgPv, whereas most elements substitute onto the Mg-site, which is consistent with a charge-compensating coupled substitution mechanism. MgPv/melt partition coefficients for Mg (D_Mg) and Si (D_Si) are related to the melt Mg/Si ratio such that D_Si becomes lower than D_Mg at low Mg/Si melt ratios. We use a crystal fractionation model, based on upper mantle refractory lithophile element ratios, to constrain the amount of MgPv and Ca-silicate perovskite (CaPv) that could have fractionated during a Hadean magma ocean event and could still be present as a chemically distinct heterogeneity in the lower mantle today. We show that a fractionated crystal pile composed of 96% MgPv and 4% CaPv could comprise up to 13 wt% of the entire mantle.     

Geochemistry and origin of the Mirny field kimberlites,Siberia

Here we present new data from a systematic Sr, Nd, O, C isotope and geochemical study of kimberlites of Devonian age Mirny field that are located in the southernmost part of the Siberian diamondiferous province. Major and trace element compositions of the Mirny field kimberlites show a significant compositional variability both between pipes and within one diatreme. They are enriched in incompatible trace elements with La/Yb ratios in the range of (65–300). Initial Nd isotope ratios calculated back to the time of the Mirny field kimberlite emplacement (t = 360 ma) are depleted relative to the chondritic uniform reservoir (CHUR) model being 4 up to 6 ɛNd(t) units, suggesting an asthenospheric source for incompatible elements in kimberlites. Initial Sr isotope ratios are significantly variable, being in the range 0.70387–0.70845, indicating a complex source history and a strong influence of post-magmatic alteration. Four samples have almost identical initial Nd and Sr isotope compositions that are similar to the prevalent mantle (PREMA) reservoir. We propose that the source of the proto-kimberlite melt of the Mirny field kimberlites is the same as that for the majority of ocean island basalts (OIB). The source of the Mirny field kimberlites must possess three main features: It should be enriched with incompatible elements, be depleted in the major elements (Si, Al, Fe and Ti) and heavy rare earth elements (REE) and it should retain the asthenospheric Nd isotope composition. A two-stage model of kimberlite melt formation can fulfil those requirements. The intrusion of small bodies of this proto-kimberlite melt into lithospheric mantle forms a veined heterogeneously enriched source through fractional crystallization and metasomatism of adjacent peridotites. Re-melting of this source shortly after it was metasomatically enriched produced the kimberlite melt. The chemistry, mineralogy and diamond grade of each particular kimberlite are strongly dependent on the character of the heterogeneous source part from which they melted and ascended.

     

Geochemical behaviours of chemical elements during subduction-zone metamorphism and geodynamic significance

ABSTRACT

Seafloor subduction and subduction-zone metamorphism (SZM) are understood to be the very cause of both subduction-zone magmatism and mantle compositional heterogeneity. In this article, we compile geochemical data for blueschist and eclogite facies rocks from global palaeo-subduction-zones in the literature, including those from the Chinese Western Tianshan ultrahigh pressure (UHP) metamorphic belt. We synthesize our up-to-date understanding on how chemical elements behave and their controls during subduction-zone metamorphism. Although the compositional heterogeneity of metamorphic minerals from subducted rocks has been recently reported, we emphasize that the mineral compositional heterogeneity is controlled by elemental availability during mineral growth, which is affected by the protolith composition, the inherited composition of precursor minerals, and the competition with neighbouring growing minerals. In addition, given the likely effects of varying protolith compositions and metamorphic conditions on elemental behaviours, we classify meta-mafic rocks from global palaeo-subduction-zones with varying metamorphic conditions into groups in terms of their protolith compositions (i.e. ocean island basalt (OIB)-like, enriched mid-ocean ridge basalt (MORB)-like, normal [N]-MORB-like), and discuss geochemical behaviours of chemical elements within these co-genetic groups rather than simply accepting the conclusions in the literature. We also discuss the geochemical consequences of SZM with implications for chemical geodynamics, and propose with emphasis that: (1) the traditionally accepted ‘fluid flux induced-melting’ model for arc magmatism requires revision; and (2) the residual subducted ocean crust cannot be the major source material for OIB, although it can contribute to the deep mantle compositional heterogeneity. We also highlight some important questions and problems that need further investigations, e.g. complex subduction-zone geochemical processes, different contributions of seafloor subduction and resultant subduction of continental materials, and the representativeness of studied HP–UHP metamorphic rocks.     

Magmatic processes in the Bishop Tuff rhyolitic magma based on trace elements in melt inclusions and pumice matrix glass

To investigate the origin of compositional zonation in the Bishop Tuff magma body, we have analyzed trace elements in the matrix glass of pumice clasts and in quartz-hosted melt inclusions. Our results show contrasting patterns for quartz in different parts of the Bishop Tuff. In all samples from the early part of the eruption, trace element compositions of matrix glasses are similar to but slightly more evolved than quartz-hosted melt inclusions. This indicates a cogenetic relationship between quartz crystals and their surrounding matrix glass, consistent with in situ crystallization. The range of incompatible element concentrations in melt inclusions and matrix glass from single pumice clasts requires 16–20 wt% in situ crystallization. This is greater than the actual crystal content of the pumices (<15 % crystals). In contrast to the pattern for the early pumices, pyroclastic flow samples from the middle part of the eruption show contrasting trends: In some clasts, the matrix is more evolved than the inclusions, whereas in other clasts, the matrix is less evolved. In the late Bishop Tuff, all crystal-rich samples have matrix glasses that are less evolved than the melt inclusions. Trace element abundances indicate that the cores of quartz in the late Bishop Tuff crystallized from more differentiated rhyolitic magma that was similar in many ways, yet distinct from the early-erupted Bishop Tuff. Our results are compatible with a model of secular incremental zoning (Hildreth and Wilson in Compositional zoning of the Bishop Tuff. J Petrol 48(5):951–999, 2007), in which melt batches from underlying crystal mush rise to various levels in a growing magma body according to their buoyancy. Early- and middle-erupted quartz crystallized from highly evolved rhyolitic melt, but then some parts of the middle-erupted magma were invaded by less differentiated rhyolite such that the matrix melt at the time of eruption was less evolved than the melt inclusions. A similar process occurred but to a greater extent in magma that erupted to form the late Bishop Tuff. In addition, there was a final, major magma mixing event in the late magma that formed Ti-rich rims on quartz and Ba-rich rims on sanidine, trapped less evolved rhyolitic melt inclusions, and resulted in dark and swirly crystal-poor pumice that is a rare type throughout much of the Bishop Tuff.     

Chemical and phase heterogeneity of Ti-Fe-Mn-silica microspherules in crushed ore samples

A Fe-Ti-Mn-silicate microspherule from the heavy mineral fraction of crushed geological samples from an underground mine (Kellyam gold deposit, Yakutia) was examined by transmission electron microscopy. The 400-μm microspherule has a complex chemical composition and contains the following elements (in order of decreasing content): O, Ti, Si, Mn, Fe, Al, Mg, Ca, and K. The material of the micro-spherule shows a polyphase structure and chemical heterogeneity with separation into amorphous oxide-silicate (SiO₂) and crystalline metallic (α-Ti + FeTi) constituents. The spherical shape and the character of internal heterogeneity suggest that the microspherule was formed owing to the rapid solidification of a melt droplet. The nanoscale heterogeneity of the microspherule is a consequence of a two-stage process. (1) Liquid immiscibility in the initial melt droplet before its solidification resulted in the incomplete spatial separation of Si + Al and Ti + Fe + Mn and appearance of SiO₂ globules with admixtures of Al, Ca, K, Mg, Ti, Fe, and Mn approximately 100 nm in size. (2) Chemical heterogeneity developed subsequently both within the globules and within the matrix at the stage of melt solidification or after the solidification. The second-stage chemical heterogeneity was manifested in (a) the separation of heavy minor element oxides (Ti, Fe, and Mn) from the light elements Si, Al, K, Ca, and Mg(?) within the globules and (b) the separation of the matrix material into crystalline metallic (α-Ti + FeTi) and amorphous oxide-silicate [SiO₂-MgO-Mn₃O₄(?)-Fe₂O₃(?)-TiO₂(?)] parts. The obtained results do not rule out the possibility of formation of such microspherules during drilling operations.     

Trace element and Pb–B–Li isotope systematics of olivine-hosted melt inclusions: insights into source metasomatism beneath Stromboli (southern Italy)

We studied the elemental and isotopic (Pb, B and Li isotopes) composition of melt inclusions hosted in highly forsteritic (Fo_83–91) olivines that were collected from San Bartolo lava and pumice (ST79p, ST82p and ST531p) samples erupted by Stromboli in historical times. The studied melt inclusions have primitive calcalkaline to shoshonitic basaltic compositions. They cover a compositional range far wider than that exhibited by the whole-rocks and differ in key trace element ratios. San Bartolo melt inclusions are characterized by lower incompatible trace element abundances, higher ratios between fluid-mobile (B, Pb, U and LILE) and less fluid-mobile (REE, Th, HFSE) elements and lower La/Yb ratios relative to the pumice-hosted melt inclusions and pumiceous melts erupted during paroxysmal events. Trace elements, along with different Pb, B and Li isotopic signatures, attest to source heterogeneity on the small scale and provide new insights into subducted components beneath Stromboli. Results of a mixing model suggest that metasomatism of the mantle source of pumice-hosted melt inclusions was driven by solute-rich high-pressure fluids (<20%) expelled from the deep portion of the slab. Heterogeneous Pb isotopic composition together with light δ¹¹B (−8.6 to −13.7‰) and δ⁷Li (+2.3 to −1.7‰) indicates that high-pressure liquids were released in variable proportions from highly dehydrated metabasalts and metasediments. On the other hand, the elemental and isotopic (δ¹¹B ~ −1.9 to −5.9‰) composition of San Bartolo melt inclusions is better explained by the addition of a prevalent aqueous component (~2 to 4%) escaped at shallower depths from sediments and altered basaltic crust in almost equivalent proportions, with a smaller contribution by high-pressure fluids. Owing to the high-angle dip of the subducted cold Ionian slab, aqueous fluids and high-pressure fluids would rise through the mantle wedge and locally superimpose on each other, thus giving origin to variously metasomatized mantle domains.     

Kinetic effects on trace element partitioning

Kinetic effects on trace element partitioning have been measured for anorthite, forsterite, and diopside grown from synthetic compositions doped with REE. A seeding technique allowed determination of crystal growth rates and partitioning information was obtained from electron microprobe analyses. Compositional deviations from equilibrium values were sought in the crystals and as gradients in the quenched liquids adjacent to the crystals. The principal result is that large deviations in trace element distribution coefficients from equilibrium values do not occur because of a compensating effect. Rapid growth depletes the melt adjacent to the crystal in the elements of which the crystal is composed, leading to different values for apparent distribution coefficients. However, as the boundary layer melt becomes depleted in the components of the crystal, growth slows and the size of the compositional perturbations decreases. Crystals grown at very high rates (e.g., > 0.2 μm/sec for diopside) tended to be too small for accurate microprobe analyses, but are probably not compositionally extreme since the melts adjacent to the crystals did not acquire sizable compositional gradients. At moderately high growth rates (e.g., 0.02 μm/sec), crystals form in the presence of boundary layer compositions perturbed by as much as 10% from bulk melt values and, in diopside, attain concentrations for excluded trace elements about 70% higher than equilibrium values for crystals plus bulk melt. At the slower growth rates typical of igneous systems, kinetic effects on trace element partitioning are probably negligible.     

Dissolution of orthopyroxene in basanitic magma between 0.4 and 2 GPa: further implications for the origin of Si-rich alkaline glass inclusions in mantle xenoliths

A large body of recent work has linked the origin of Si-Al-rich alkaline glass inclusions to metasomatic processes in the upper mantle. This study examines one possible origin for these glass inclusions, i.e., the dissolution of orthopyroxene in Si-poor alkaline (basanitic) melt. Equilibrium dissolution experiments between 0.4 and 2 GPa show that secondary glass compositions are only slightly Si enriched and are alkali poor relative to natural glass inclusions. However, disequilibrium experiments designed to examine dissolution of orthopyroxene by a basanitic melt under anhydrous, hydrous and CO₂-bearing conditions show complex reaction zones consisting of olivine, ± clinopyroxene and Si-rich alkaline glass similar in composition to that seen in mantle xenoliths. Dissolution rates are rapid and dependent on volatile content. Experiments using an anhydrous solvent show time dependent dissolution rates that are related to variable diffusion rates caused by the saturation of clinopyroxene in experiments longer than 10 minutes. The reaction zone glass shows a close compositional correspondence with natural Si-rich alkaline glass in mantle-derived xenoliths. The most Si-and alkali-rich melts are restricted to pressures of 1 GPa and below under anhydrous and CO₂-bearing conditions. At 2 GPa glass in hydrous experiments is still Si-␣and alkali-rich whereas glass in the anhydrous and CO₂-bearing experiments is only slightly enriched in SiO₂ and alkalis compared with the original solvent. In the low pressure region, anhydrous and hydrous solvent melts yield glass of similar composition whereas the glass from CO₂-bearing experiments is less SiO₂ rich. The mechanism of dissolution of orthopyroxene is complex involving rapid incongruent breakdown of the orthopyroxene, combined with olivine saturation in the reaction zone forming up to 60% olivine. Inward diffusion of CaO causes clinopyroxene saturation and uphill diffusion of Na and K give the glasses their strongly alkaline characteristics. Addition of Na and K also causes minor SiO₂ enrichment of the reaction glass by increasing the phase volume of olivine. Olivine and clinopyroxene are transiently stable phases within the reaction zone. Clinopyroxene is precipitated from the reaction zone melt near the orthopyroxene crystal and redissolved in the outer part of the reaction zone. Olivine defines the thickness of the reaction zone and is progressively dissolved in the solvent as the orthopyroxene continues to dissolve. Although there are compelling reasons for supporting the hypothesis that Si-rich alkaline melts are produced in the mantle by orthopyroxene – melt reaction in the mantle, there are several complications particularly regarding quenching in of disequilibrium reaction zone compositions and the mobility of highly polymerized melts in the upper mantle. It is considered likely that formation of veins and pools of Si-rich alkaline glass by orthopyroxene – melt reaction is a common process during the ascent of xenoliths. However, reaction in situ within the mantle will lead to equilibration and therefore secondary melts will be only moderately siliceous and alkali poor. Received: 24 August 1998 / Accepted: 2 December 1998     

Concentration of ore elements in magmatic melts and natural fluids as deduced from data on inclusions in minerals

Based on intergration of the published data on composition of inclusions in minerals and quenched glasses, the mean concentrations of 24 ore elements have been calculated for magmatic silicate melts formed in main geodynamic settings of the Earth and in natural fluids. The mean glass compositions normalized to the primitive mantle correlate with the partition coefficient between olivine and the basic melt. It is established that the degree of enrichment in ore elements depending on geodynamic setting is controlled by various contribution of fluids to the element transfer and accumulation. The ratios of element contents in each geodynamic setting to the mean concentrations of elements over all settings in the Earth have been calculated.     

Spinel peridotite xenoliths from the Atsagin-Dush volcano, Dariganga lava plateau, Mongolia: a record of partial melting and cryptic metasomatism in the upper mantle

Spinel peridotite xenoliths from the Atsagin-Dush volcanic centre, SE Mongolia range from fertile lherzolites to clinopyroxene(cpx)-bearing harzburgites. The cpx-poor peridotites typically contain interstitial fine-grained material and silicate glass and abundant fluid inclusions in minerals, some have large vesicular melt pockets that apparently formed after primary clinopyroxene and spinel. No volatile-bearing minerals (amphibole, phlogopite, apatite, carbonate) have been found in any of the xenoliths. Fifteen peridotite xenoliths have been analysed for major and trace elements; whole-rock Sr isotope compositions and O isotope composition of all minerals were determined for 13 xenoliths. Trace element composition and Sr-Nd isotope compositions were also determined in 11 clinopyroxene and melt pocket separates. Regular variations of major and moderately incompatible trace elements (e.g. heavy-rare-earth elements) in the peridotite series are consistent with its formation as a result of variable degrees of melt extraction from a fertile lherzolite protolith. The Nd isotope compositions of LREE (light-rare-earth elements)-depleted clinopyroxenes indicate an old (≥ 1 billion years) depletion event. Clinopyroxene-rich lherzolites are commonly depleted in LREE and other incompatible trace elements whereas cpx-poor peridotites show metasomatic enrichment that can be related to the abundance of fine-grained interstitial material, glass and fluid inclusions in minerals. The absence of hydrous minerals, ubiquitous CO₂-rich microinclusions in the enriched samples and negative anomalies of Nb, Hf, Zr, and Ti in primitive mantle-normalized trace element patterns of whole rocks and clinopyroxenes indicate that carbonate melts may have been responsible for the metasomatic enrichment. Low Cu and S contents and high δ³⁴S values in whole-rock peridotites could be explained by interaction with oxidized fluids that may have been derived from subducted oceanic crust. The Sr-Nd isotope compositions of LREE-depleted clinopyroxenes plot either in the MORB (mid-ocean-ridge basalt) field or to the right of the mantle array, the latter may be due to enrichment in radiogenic Sr. The LREE-enriched clinopyroxenes and melt pockets plot in the ocean island-basalt field and have Sr-Nd isotope signatures consistent with derivation from a mixture of the DMM (depleted MORB mantle) and EM (enriched mantle) II sources. Received: 18 January 1996 / Accepted: 23 August 1996     

南堡凹陷沉积岩化学元素分布特征及多元统计方法研究

对南堡凹陷Ed₁亚段、Ng_下、Ng_上、Nm_底地层的75个沉积岩样品进行了主量、微量元素分析,结果表明粒度效应造成砂岩和泥岩元素丰度明显不同,砂岩除富集K、Na、Sr、Ba、Si外,其余元素均较泥岩亏损.根据地层垂向上元素丰度由高—低—高的变化规律,可将这4个亚段分为Ed₁、Ng_下和Ng_上、Nm_底3个阶段,与凹陷构造演化特征响应.因子分析、聚类分析等多元统计方法表明,表生环境中元素具有不同的迁移富集规律,Ca、Na、Sr等具有较强的活动性,Zr、Hf等少数元素则在粗粒级中含量较高,而其余元素则多在黏土粒级中富集.元素在表生环境中地球化学行为的不同主要受化学结构特征控制,沉积环境对其也有影响.     

Multi-Elemental Analysis of ATHO-G Rhyolitic Glass (MPI-DING Reference Material) by Femtosecond and Nanosecond LA-ICP-MS: Evidence for Significant Heterogeneity of B,V, Zn,Mo, Sn,Sb, Cs,W, Pt and Pb at the Millimetre Scale

This paper reports on the application of variants of LA-ICP-MS – including infrared femtosecond laser ablation (fs-LA) inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and nanosecond laser ablation (ns-LA) coupled with single-collector sector-field (SF-) ICP-MS – to the in situ determination of trace elements in different splits of the reference material (RM) ATHO-G (MPI-DING). Analyses of the materials performed by fs- and ns-LA-ICP-MS demonstrated the efficiency of the techniques with typical accuracy at a level of ≤ ± 20%. One ‘anomalous’ split, however, displayed a significant discrepancy from the reference concentrations for B, V, Zn, Mo, Sn, Sb, Cs, W and Pb. Three- to six-fold enrichment of V, Mo, Cs and Pt relative to the reference contents in this split is likely to have been due to direct contact of the silicate melt with Pt crucible walls and ceramics. Boron, Zn, Sn, Sb, W and Pb depletion relative to the reference concentrations is probably due to siderophile element adsorption by the Pt walls and/or related to the formation of volatile-depleted compositional cords during the preparation process. Our results imply that additional precautions should be taken against volatile/siderophile element heterogeneity in marginal/surface layers (≤ 10 mm) during the preparation of RMs by the fusion technique.     

Local and regional variation of MORB parent magmas: evidence from melt inclusions from the Endeavour Segment of the Juan de Fuca Ridge

The development of petrogenetic models of igneous processes in the mantle is dependent on a detailed knowledge of the diversity of magmas produced in the melting regime. These primary magmas, however, undergo significant mixing and fractionation during transport to the surface, destroying much of the evidence of their primary diversity. To circumvent this problem and to determine the diversity of melts produced in the mantle, we used melt inclusions hosted in primitive plagioclase phenocrysts from eight mid-ocean ridge basalts from the axial and West Valleys of the Endeavour Segment, Juan de Fuca Ridge. This area was selected for study because of the demonstrated close association of enriched (E-MORB) lavas and incompatible element enriched depleted (N-MORB) lavas. Rehomogenized melt inclusions from E-MORB, T-MORB, and N-MORB lavas have been analyzed by electron and ion microprobe for major and trace elements. The depleted and enriched lavas, as well as their melt inclusions, have very similar compatible element concentrations (major elements, Sr, Ni and Cr). Inclusion compositions are more primitive than, yet collinear with, the host lava suites. In contrast, the minor and trace element characteristics of melt inclusions from depleted and enriched lavas are different both in range and absolute concentration. N-MORB lavas contain both depleted and enriched melt inclusions, and therefore exhibit the largest compositional range (K₂O: 0.01 to 0.4 oxide wt%, P₂O₅: <0.01 to 0.2 oxide wt%, La_N: 7 to 35, Yb_N: 1 to 13, and Ti/Zr: <100 to 1300). E-MORB lavas contain only enriched inclusions, and are therefore relatively homogeneous (K₂O: 0.32 to 0.9 oxide wt %, P₂O₅: 0.02 to 0.35 oxide wt%, La_N: 11 to 60, Yb_N: 4 to 21, and Ti/Zr: ∼100). In addition, the most primitive E-32 inclusions are similar in composition to the most enriched inclusions from the depleted hosts. Major element data for melt inclusions from both N-MORB and E-MORB lavas suggest that the magmas lie on a low pressure cotectic, consistent with a petrogenesis including fractional crystallization. However, the minor and trace element compositions in melt inclusions vary independently of the major element composition implying an alternative history. When fractionation-corrected, inclusion compositions correlate with their host glass composition. Hence, the degree of enrichment of the lavas is a function of the composition of aggregated melts, not of processing in the upper mantle or lower crust. Based on this fact, the lava suites are not produced from a single parent magma, but from a suite of primary magmas. The chemistry of the melt inclusions from the enriched lavas is consistent with a derivation from variable percentages of partial melting within the spinel stability field by a process of open system (continuous or critical) melting assuming a depleted lherzolite source veined with clinopyroxenite. The low percentage melts are dominantly enriched melts of the clinopyroxenite. In contrast, the depleted lavas were created by melting of a harzburgite source, possibly fluxed with a fluid enriched in K, Ba and the LREE. Such a source was likely melted up to or past the point at which all of its clinopyroxene was consumed. This set of characteristics is consistent with a scenario by which diverse melts produced at different depths travel through the melting regime to the base of the crust without homogenizing en route. The homogeneous major element characteristics are created in the lower crust by fractional crystallization and reaction with lower crustal gabbros. Therefore, the degree of decoupling between major and trace element characteristics of the melt inclusions (and lavas) is dictated by the reaction rate of the melts with the materials in the conduit walls, as well as the residence times and flux rate, in the upper mantle and lower crust. Received: 2 December 1997 / Accepted: 27 August 1998     

The trace element compositions of S-type granites: evidence for disequilibrium melting and accessory phase entrainment in the source

Within individual plutons, the trace element concentrations in S-type granites generally increase with maficity (total iron and magnesium content and expressed as atomic Fe + Mg in this study); the degree of variability in trace element concentration also expands markedly with the same parameter. The strongly peraluminous, high-level S-type granites of the Peninsular Pluton (Cape Granite Suite, South Africa) are the product of biotite incongruent melting of a metasedimentary source near the base of the crust. Leucogranites within the suite represent close to pure melts from the anatectic source and more mafic varieties represent mixtures of melt and peritectic garnet and ilmenite. Trace elements such as Rb, Ba, Sr and Eu, that are concentrated in reactant minerals in the melting process, show considerable scatter within the granites. This is interpreted to reflect compositional variation in the source. In contrast, elements such as LREE, Zr and Hf, which are concentrated within refractory accessory phases (zircon and monazite), show well-defined negative correlations with increasing SiO₂ and increase linearly with increasing maficity. This is interpreted to reflect coupled co-entrainment of accessory minerals and peritectic phases to the melt: leucocratic rocks cannot have evolved from the more mafic compositions in the suite by a process of fractional crystallisation because in this case they would have inherited the zircon-saturated character of this hypothetical earlier magma. Trace element behaviour of granites from the Peninsular Pluton has been modelled via both equilibrium and disequilibrium trace element melting. In the disequilibrium case, melts are modelled as leaving the source with variable proportions of entrained peritectic phases and accessory minerals, but before the melt has dissolved any accessory minerals. Thus, the trace element signature of the melt is largely inherited from the reactants in the melting reaction, with no contribution from zircon and monazite dissolution. In the equilibrium case, melt leaves the source with entrained crystals, after reaching zircon and monazite saturation. A significant proportion of the rocks of the Peninsular Pluton have trace element concentrations below those predicted by zircon and monazite saturation. In the case of the most leucocratic rocks all compositions are zircon undersaturated; whilst the majority of the most mafic compositions are zircon oversaturated. However, in both cases, zircon is commonly xenocrystic. Thus, the leucocratic rocks represent close to pure melts, which escaped their sources rapidly enough that some very closely match the trace element disequilibrium melting model applied in this study. Zircon dissolution rates allow the residency time for the melt in the source to be conservatively estimated at less than 500 years.