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1.
This work presents new trace element and petrographic data for three forsterite-bearing, Ca-Alrich inclusions from the Allende meteorite: TE, 818a, and 110-A. Such inclusions form a continuum with Type B1 and B2 Ca-Al-rich inclusions (CAIs), and we refer to them as “Type B3” CAIs. Textures, mineral chemistries, crystal-chemically fractionated REE patterns, and other properties suggest that Type B3 crystallized from partly molten evaporative residues. The concentrations of refractory lithophile elements are lower than in Type B1 and Type B2, in approximately inverse proportion to the higher concentrations of Mg and Si in the Type B3's. The refractory trace element abundances of the forsterite-bearing, isotopically anomalous FUN CAIs TE and CG14 suggest that they formed at higher temperatures and under more oxidizing conditions than other Type B CAIs, thus strengthening the previously observed link between relatively oxidized CAI compositions and FUN properties.We also present evidence that 818a was strongly re-heated and modified in the nebula after its initial crystallization: it consists of a core of coarse-grained Ti-Al-pyroxene (Tpx), forsterite, spinel and metal grains and a thick, surrounding mantle of melilite that has been almost totally converted to fine-grained alteration products. In the core, the mean concentrations of refractory lithophiles and siderophiles are similar (both ~ 14 × CI), but in the mantle, the refractory siderophiles are a factor of 2 lower (~ 9 × CI) than the refractory lithophiles (~18 × CI). Because the core and mantle display similar, mineralogically-fractionated REE patterns (both sloping up from La to Lu), the pre-alteration mantle could not have formed during fractional crystallization of the primary CAI nor as a later condensate over the core. A 3-stage formation process is required for 818a: (1) crystallization of the primary CAI rich in Tpx throughout; (2) re-heating and partial volatilization of Mg and Si from the outer portion of the CAI, causing an increase in the concentration of refractory lithophiles, a loss of siderophiles, and converting Tpx to melilite; (3) metasomatic alteration of the melilite-rich mantle.  相似文献   

2.
The concentrations and isotopic compositions of lithium, beryllium, and boron, analyzed in situ by ion microprobe in 66 spots of a type B1 Ca-Al-rich inclusion (CAI 3529-41) from the Allende meteorite, are reported. Large variations are observed for both the Li and the B isotopic ratios with 7Li/6Li ranging from 9.2 ± 0.22 to 12.22 ± 0.43 (a ≈250‰ range in δ7Li values) and 10B/11B ranging from 0.2468 ± 0.0057 to 0.4189 ± 0.0493 (a 410‰ range in δ11B values). The very low Li concentrations (<1 ppb) observed in several anorthite and fassaite grains require that a correction for the contribution of spallogenic Li produced during irradiation of the Allende meteoroid by galactic cosmic rays (GCR) be made (after this correction 7Li/6Li ranges from 9.2 ± 0.22 to 13.44 ± 0.56, i.e., a ≈350‰ range in δ7Li values). In 3529-41, the 10B/11B ratios are positively correlated with 9Be/11B in a manner indicating the in situ decay of short-lived 10Be (half-life = 1.5 Ma) with a 10Be/9Be ratio at the time of formation of the CAI of 8.8 ± 0.6 × 10−4, which is in agreement with previous findings [McKeegan, K.D., Chaussidon, M., Robert, F., 2000. Incorporation of short-lived 10Be in a calcium-aluminum-rich inclusion from the Allende meteorite. Science289, 1334-1337]. The present detailed investigation demonstrates that only minor perturbations of the 10Be-10B system are present in 3529-41, contrary to the 26Al/26Mg system for which numerous examples of isotopic redistribution following crystallization were observed [Podosek, F.A., Zinner, E.K., MacPherson, G.J., Lundberg, L.L., Brannon, J.C., Fahey, A.J., 1991. Correlated study of initial 87Sr/86Sr and Al-Mg systematics and petrologic properties in a suite of refractory inclusions from the Allende meteorite. Geochim. Cosmochim. Acta55, 1083-1110]. Petrographically based criteria were developed to identify within the 66 analyzed spots in 3529-41, those where post-magmatic perturbation of the Li and Be distributions occurred. Li and Be concentrations measured in different analytical spots are compared with those predicted by using experimentally determined partition coefficients according to a model of closed-system crystallization of the CAI melt. These criteria show that 56% of the spots in melilite, 38% in anorthite, and 8% in fassaite suffered post-crystallization perturbations of Li and/or Be distributions. In the remaining spots, which do not show obvious indication of redistribution of Li or Be, the 7Li/6Li isotopic variations (corrected for GCR exposure) are positively correlated with9Be/6Li suggesting the in situ decay of now-extinct 7Be. The derived isochron implies that at the time of its formation, the CAI melt had a 7Be/9Be ratio of 0.0061 ± 0.0013 and a 7Li/6Li ratio of 11.49 ± 0.13. In contrast, all the spots in 3529-41, which do show evidence for post-magmatic redistribution of Li and Be, have relatively constant 7Li/6Li, averaging 11.72 ± 0.56, which is consistent with mass balance calculations for Li isotopic homogenization in the CAI after the decay of 7Be. The incorporation of live 7Be in 3529-41 requires, because of the very short half-life of this nuclide (53 days), that it be produced essentially contemporaneously with the formation of the CAI. Therefore, the irradiation processes responsible for production of 7Be must have occurred within the solar accretion disk. Calculations developed in the framework of the x-wind model [Gounelle, M., Shu, F.H., Shang, H., Glassgold, A.E., Rehm, E.K., Lee, T., 2004. The origin of short-lived radionuclides and early Solar System irradiation (abstract). Lunar Planet. Sci.35, 1829] reproduce the 7Be and 10Be abundances observed in 3529-41. The correlated presence of 7Be and 10Be in 3529-41 is thus a strong argument that 10Be, which is observed rather ubiquitously in CAIs, is also a product of irradiation in the early solar system, as might be a significant fraction of other short-lived radionuclides observed in early solar system materials.  相似文献   

3.
The oxygen isotopic micro-distributions within and among minerals in a coarse-grained Ca, Al-rich inclusion (CAI), 7R-19-1 from the Allende meteorite, were measured by in situ using secondary ion mass spectrometry (SIMS). All values of O isotopic ratios in 7R-19-1 minerals fall along the carbonaceous chondrite anhydrous mineral mixing (CCAM) line on a δ17OSMOW vs. δ18OSMOW plot. Major refractory minerals (spinel, fassaite and melilite) in 7R-19-1 showed large negative anomalies of Δ17O in the order, spinel (−21‰) > 16O-rich melilite (∼−18‰) > fassaite (−15 to +1‰) > 16O-poor melilite (−8 to +2‰). However, the lower limit values of Δ17O are similar at about −21‰, a value commonly observed in CAIs. The similarity in the extreme values of the isotope anomaly anomalies suggests that crystallization of all CAIs started from an 16O enrichment of 21‰ (Δ17O) relative to terrestrial values. The order of the O isotopic anomalies observed for 7R-19-1, except for 16O-poor melilite, is parallel to the crystallization sequence determined by experiment from CAI liquid (Stolper, 1982), indicating that the O isotopic exchange in 7R-19-1 occurred between CAI melt and surrounding gas while 7R-19-1 was crystallizing from the 16O enriched CAI liquid (∼−21‰ in Δ17O) in the 16O-poor solar nebula. However, the a single crystallization sequence during the cooling stage cannot explain the existence of 16O-poor melilite. The presence of 16O-poor melilite suggests that multiple heating events occurred during CAI formation. The sharp contact between 16O-rich and 16O-poor melilite crystals and within 16O-rich melilite indicates that these multiple heatings occurred quickly. Based on the O isotopic and chemical compositions, fassaite crystals were aggregates of relic crystals formed from CAI melt whichthat have had various O isotopic compositions from the remelting processes. The results of intra-mineral distributions of O isotopes also support multiple heating events during CAI formation.  相似文献   

4.
Textural and chemical features of five coarse-grained, calcium-aluminum-rich inclusions from the Allende meteorite indicate that some of the melilite in these inclusions was formed by a secondary metamorphic event and not by primary crystallization from a melt or by a sequential nebular condensation process. These inclusions contain embayed pyroxene surrounded by melilite. Physically separated pyroxene crystals are often in optical continuity indicating that they were once part of larger single crystals that have been partly replaced by melilite. Other evidences of metamorphism include reaction textures between melilite and spinel, and metamorphic textures such as kink-band-like features, lobate sutured grain boundaries, and 120° triple-points. This type of metamorphic process requires the addition of Ca which we propose came from calcite or by introduction of a fluid phase. We believe that the most likely environment for this metamorphic process is on a small planetary body, and not in the solar nebula. The results of this study are compatible with oxygen isotopic heterogeneities within CAI, and provide a mechanism for producing lower temperature alteration phases and the rim phases found in these inclusions. We conclude that planetary processes must thus be considered in the formation history of CAI, and that it is necessary to reconsider the classification system of these objects in light of the replacement process proposed here.  相似文献   

5.
Inclusion 101.1 from the CV3 carbonaceous chondrite Efremovka is a compact Type A Ca-Al-rich inclusion (CAI) highly enriched in ultrarefractory (UR) oxides. It is the first complete CAI with a UR rare earth element (REE) pattern found in a CV3 chondrite. The inclusion is petrographically complex and was formed in a multistage process. It consists of several lithologically unrelated units.The core contains abundant Y- and Zr-perovskite, Sc- and Zr-rich fassaite, and metallic FeNi enclosed in melilite. All mineral species (except spinel) in all lithological units exhibit the same basic UR REE pattern. Four different populations of perovskites are distinguished by different Y/Zr ratios. A few of the perovskites have Y/Zr ratios similar to those obtained from crystal/liquid fractionation experiments. Perovskites from the other three populations have either chondritic, lower than chondritic Y/Zr ratios or extremely low Zr contents. Ca isotopic ratios differ among three perovskites from different populations, demonstrating a variety of sources and formational processes. Most fassaites crystallized in situ through reaction between the CAI liquid and preexisting perovskites. This process induced redistribution of Zr, Y, Sc, and V between perovskite and fassaite, thus overprinting the original abundances in perovskite. Fassaite reaction rims around FeNi metals are also encountered. They are enriched in V, which was gained from the metal through oxidation of V in metal during fassaite crystallization. The relative abundances of Zr, Y, and Sc in perovskites are complementary to the abundances of these elements in Sc- and Zr-fassaite, indicating subsolidus partitioning of these elements between the two phases. Perovskites are enriched in Y and depleted in Sc and Zr in comparison to fassaites.The core contains two complete captured CAIs, several sinuous fragments, and fine-grained polygonal refractory fragments. An assemblage of andradite-wollastonite-hedenbergite and pure metallic iron is encountered as enclaves in the interior of some sinuous fragments. Metallic Fe and wollastonite formed by reduction of preexisting andradite and hedenbergite nebular alteration products upon inclusion in the highly reduced CAI melt. Numerous spinel clusters and framboids with varying V2O3 and Cr2O3 concentrations are enclosed in individual melilite crystals in the host CAI and captured CAIs. The rim sequence of the host consists of six layers (from the inside outward): (a) FeO-poor spinel, (b) Sc-bearing fassaite, (c) Al-diopside, (d) Al- and Ca-bearing olivine, (e) pure diopside, and (f) Ca-poor olivine. Like the constituents of the CAI core, all mineral layers of the rim sequence, except spinel, have the same UR REE pattern. However, the total REE abundances decrease systematically by 1 order of magnitude from layer 2 to layer 6. This feature strongly suggests formation of the rim sequence by successive condensation from a unique reservoir enriched in UR elements and excludes formation by flash heating. Petrography, mineral chemistry, REE, refractory lithophile element abundances, and Ca isotopic compositions demonstrate the complex multistage formation history of a CAI that on the surface looks like a regular Type A inclusion.  相似文献   

6.
Type B CAIs are subdivided into B1s, with well-developed melilite mantles, and B2s, with randomly distributed melilite. Despite intensive study, the origin of the characteristic melilite mantle of the B1s remains unclear. Recently, we proposed that formation of the melilite mantle is caused by depletion of the droplet surface in volatile magnesium and silicon due to higher evaporation rates of volatile species compared to their slow diffusion rates in the melt, thus making possible crystallization of melilite at the edge of the CAI first, followed by its crystallization in the central parts at lower temperatures. Here, we present the results of an experimental study that aimed to reproduce the texture observed in natural Type B CAIs. First, we experimentally determined crystallization temperatures of melilite for three melt compositions, which, combined with literature data, allowed us to find a simple relationship between the melt composition, crystallization temperature, and composition of first crystallizing melilite. Second, we conducted a series of evaporation and cooling experiments exposing CAI-like melts to gas mixtures with different oxygen fugacities (fO2). Cooling of the molten droplets in gases with logfO2?IW-4 resulted in crystallization of randomly distributed melilite, while under more reducing conditions, melilite mantles have been formed. Chemical profiles through samples quenched right before melilite started to crystallize showed no chemical gradients in samples exposed to relatively oxidizing gases (logfO2?IW-4), while the near-surface parts of the samples exposed to very reducing gases (logfO2?IW-7) were depleted in volatile MgO and SiO2, and enriched in refractory Al2O3. Using these experimental results and the fact that the evaporation rate of magnesium and silicon from CAI-like melts is proportional to , we estimate that Type B1 CAIs could be formed by evaporation of a partially molten precursor in a gas of solar composition with . Type B2 CAIs could form by slower evaporation of the same precursors in the same gas with .  相似文献   

7.
Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO5) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.  相似文献   

8.
The coarse-grained, igneous, anorthite-rich (Type C) CAIs from Allende studied (100, 160, 6-1-72, 3529-40, CG5, ABC, TS26, and 93) have diverse textures and mineralogies, suggesting complex nebular and asteroidal formation histories. CAIs 100, 160, 6-1-72, and 3529-40 consist of Al,Ti-diopside (fassaite; 13-23 wt% Al2O3, 2-14 wt% TiO2), Na-bearing åkermanitic melilite (0.1-0.4 wt% Na2O; Åk30-75), spinel, and fine-grained (∼5-10 μm) anorthite groundmass. Most of the fassaite and melilite grains have “lacy” textures characterized by the presence of abundant rounded and prismatic inclusions of anorthite ∼5-10 μm in size. Lacy melilite is pseudomorphed to varying degrees by grossular, monticellite, and pure forsterite or wollastonite. CAI 6-1-72 contains a relict Type B CAI-like portion composed of polycrystalline gehlenitic melilite (Åk10-40), fassaite, spinel, perovskite, and platinum-group element nuggets; the Type B-like material is overgrown by lacy melilite and fassaite. Some melilite and fassaite grains in CAIs 100 and 160 are texturally similar to those in the Type B portion of 6-1-72. CAIs ABC and TS26 contain relict chondrule fragments composed of forsteritic olivine and low-Ca pyroxene; CAI 93 is overgrown by a coarse-grained igneous rim of pigeonite, augite, and anorthitic plagioclase. These three CAIs contain very sodium-rich åkermanitic melilite (0.4-0.6 wt% Na2O; Åk63-74) and Cr-bearing Al,Ti-diopside (up to 1.6 wt% Cr2O3, 1-23 wt% Al2O, 0.5-7 wt% TiO2). Melilite and anorthite in the Allende Type C CAI peripheries are replaced by nepheline and sodalite, which are crosscut by andradite-bearing veins; spinel is enriched in FeO. The CAI fragment CG5 is texturally and mineralogically distinct from other Allende Type Cs. It is anorthite-poor and very rich in spinel poikilitically enclosed by Na-free gehlenitic melilite (Åk20-30), fassaite, and anorthite; neither melilite nor pyroxene have lacy textures; secondary minerals are absent. The Al-rich chondrules 3655b-2 and 3510-7 contain aluminum-rich and ferromagnesian portions. The Al-rich portions consist of anorthitic plagioclase, Al-rich low-Ca pyroxene, and Cr-bearing spinel; the ferromagnesium portions consist of fosteritic olivine, low-Ca pyroxene, and opaque nodules.We conclude that Type C CAIs 100, 160, 6-1-72, and 3529-40 formed by melting of coarse-grained Type B-like CAIs which experienced either extensive replacement of melilite and spinel mainly by anorthite and diopside (traces of secondary Na-bearing minerals, e.g., nepheline or sodalite, might have formed as well), or addition of silica and sodium during the melting event. CG5 could have formed by melting of fine-grained spinel-melilite CAI with melilite and spinel partially replaced anorthite and diopside. CAIs ABC, 93, and TS-26 experienced melting in the chondrule-forming regions with addition of chondrule-like material, such as forsteritic olivine, low-Ca pyroxene, and high-Ca pyroxene. Anorthite-rich chondrules formed by melting of the Al-rich (Type C CAI-like) precursors mixed with ferromagnesian, Type I chondrule-like precursors. The Allende Type C CAIs and Al-rich chondrules experienced fluid-assisted thermal metamorphism, which resulted in pseudomorphic replacement of melilite and anorthite by grossular, monticellite, and forsterite (100, 160, 6-1-72, 3592-40) or by grossular, monticellite, and wollastonite (ABC, 93, TS-26). The pseudomorphic replacement was followed or accompanied by iron-alkali metasomatic alteration resulting in replacement of melilite and anorthite by nepheline and sodalite, enrichment of spinel in FeO, and precipitation of salite-hedenbergite pyroxenes, wollastonite, and andradite in fractures and pores in and around CAIs.  相似文献   

9.
Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO2-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO2 at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000  相似文献   

10.
Analyses of trace elements in the mineral phases of granulites provide important information about the trace element distribution in the lower crust. Since granulites are often considered residues of partial melting processes, trace element characteristics of their mineral phases may record mineral/melt equilibria thus giving an opportunity to understand the nature and composition of melts in the lower continental crust. This study provides an extensive set of mineral trace element data obtained by LA-ICP-MS analyses of mafic and intermediate granulites from Central Finland. Mass balance calculations using the analytical data indicate a pronounced contribution of the accessory minerals apatite for the REE and ilmenite for the HFSE. Coherent mineral/mineral ratios between samples point to a close approach to equilibrium except for minerals intergrown with garnet porphyroblasts. Mineral trace element data were used for the formulation of a set of D mineral/melt partition coefficients that is applicable for trace element modelling under lower crustal conditions. D mineral/melt were derived by the application of predictive models and using observed constant mineral/mineral ratios. The comparison of the calculated D mineral/melt with experimental data as well as the relationship between mineral trace element contents and a leucosome with a composition close to an equilibrium melt provides additional constraints on mineral/melt partitioning. The D values derived in this study are broadly similar to magmatic partition coefficients for intermediate melt compositions. They provide a first coherent set of D values for Sc, V, Cr and Ni between clinopyroxene, amphibole, garnet, orthopyroxene, ilmenite and melt. In addition, they emphasize the strong impact that ilmenite exerts on the distribution of Nb and Ta.  相似文献   

11.
Recently Chaussidon et al. reported isotopic measurements of the Allende meteorite Ca, Al-rich inclusion (CAI) 3529-41 that they claim as evidence that live 7Be was incorporated into this CAI at the time of its formation [Chaussidon, M., Robert, F., McKeegan, K.D., 2006. Li and Be isotopic variations in an Allende CAI: evidence for the in situ decay of short-lived 10Be and for the possible presence of the short-lived nuclide 7Be in the early solar system. Geochim. Cosmochim. Acta70, 224-245]. They claim their data show excesses of 7Li/6Li above the chondritic value, and that the 7Li/6Li excesses correlate linearly with 9Be/6Li, implying that the excess 7Li arose from the decay of 7Be (t1/2 = 53 days). In this Comment we dispute this claim. We show that the authors did not statistically analyze their data correctly, and that a linear correlation between 7Li/6Li and 9Be/6Li can in fact be ruled out. We show that the authors over-corrected for the effects of spallogenic Li, and in fact no statistically significant excesses of 7Li above chondritic ratios exist. Finally, we show that many of the spots in Allende 3529-41 that the authors counted as isotopically undisturbed show evidence of isotopic disturbance. We demonstrate that while their data support the late addition of isotopically light Li in spots with low Be/Li, their data are otherwise consistent with constant 7Li/6Li at near-chondritic levels. The data do not provide support for live 7Be in the early Solar System.  相似文献   

12.
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements V, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in Fremdlinge with a spatial resolution of 15 to 25 μm. A sulfide vein in a refractory inclusion in Allende (CV3-oxidized) is enriched in Rh, Ru, and Os with no detectable Pd, Re, Ir, or Pt, indicating that Rh, Ru, and Os were redistributed by sulfidation of the inclusion, causing fractionation of Re/Os and other siderophile element ratios in Allende CAIs. Fremdlinge in compact Type-A inclusions from Efremovka (CV3-reduced) exhibit subsolidus exsolution into kamacite and taenite and minimal secondary formation of V-magnetite and schreibersite. Siderophile element partitioning between taenite and kamacite is similar to that observed previously in iron meteorites, while preferential incorporation of the light PGEs (Ru, Rh, Pd) relative to Re, Os, Ir, and Pt by schreibersite was observed. Fremdling EM2 (CAI Ef2) has an outer rim of P-free metal that preserves the PGE signature of schreibersite, indicating that EM2 originally had a phosphide rim and lost P to the surrounding inclusion during secondary processing. Most Fremdlinge have chondrite-normalized refractory PGE patterns that are unfractionated, with PGE abundances derived from a small range of condensation temperatures, ∼1480 to 1468 K at Ptot = 10−3 bar. Some Fremdlinge from the same CAI exhibit sloping PGE abundance patterns and Re/Os ratios up to 2 × CI that likely represent mixing of grains that condensed at various temperatures.  相似文献   

13.
Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998  相似文献   

14.
We report a detailed petrography, mineral chemistry, and trace element study of MaTroc, a large calcium-aluminum-rich inclusion (CAI) (5 × 2.5 mm) of irregular triangular shape. The inclusion has a zonal structure: The core consists of a porous plagioclase-olivine-Ca-rich pyroxene intergrowth with subordinate apatite. Its texture is meta-gabbro-like, similar to other plagioclase-olivine inclusions (POIs). The mantle has variable thickness (0.1-1.5 mm) and consists of a compact symplectitic intergrowth of spinel (hercynite) and plagioclase with abundant dispersed magnetite, subordinate Ca-rich pyroxene, and traces of sulfides. The thin (5-50 μm) discontinuous crust of MaTroc consists mainly of plagioclase with some olivine and magnetite.The Mg-Fe phases of MaTroc are Fe-rich: olivine has Fa33.2 and high NiO content, similar to that in the host rock, Ca-rich pyroxene has much lower TiO2 and Cr2O3 contents than that of the host chondrite, and plagioclase is An55-An74. Magnetites have variable compositions, are poorer in Al2O3 and Cr2O3 and richer in NiO than those in the host. Spinels have also variable compositions, rich in FeO, NiO, and ZnO.Despite their different mineralogy, both core and mantle have bulk trace element abundances similar to those in average group II CAIs. However, the mantle is richer in Nb and U and poorer in Eu, Be, B, Sr, and Li than the core. All minerals have high trace element contents. Minerals in the core show signs of incomplete equilibration of trace elements within and between them. Mantle minerals are far from equilibrium with each other and the bulk system. Spinel and anorthite carry the trace element signature of their precursor melilite (or hibonite), and magnetite contains large amounts of a heterogeneously distributed remnant extremely rich in trace elements (“obscurite”), possibly of a former perovskite.Inclusion MaTroc has a complex history. The POI core probably formed by reaction of an unknown precursor(s) of condensation origin with a vapor to form olivine, plagioclase, clinopyroxene, apatite, and (an) unknown phase(s) that vanished, leaving abundant void space. The spinel-rich mantle is also a secondary mineral assemblage that formed by breakdown of and solid-vapor reactions with a precursor or precursors, possibly melilite (or hibonite). The abundant magnetite formed by reaction of perovskite with an oxidizing vapor and by precipitation from such a vapor. All phases of the inclusion experienced the metasomatic addition of Fe, Ni, and moderately volatile elements such as V, Be, Li, Cr, and Mn—similar to all other constituents of the Maralinga CK chondrite. Phases in MaTroc and in the host rock are close to equilibrium in the distribution of Fe, Mg, Ni, and Mn but far from equilibrium in the distribution of M+3 and M+4 ions. The minor and trace element abundances in the magnetite of the host rock and of MaTroc preclude an origin by oxidation of a metal precursor.  相似文献   

15.
Microscopic melt inclusions found in magmatic minerals are undoubtedly one of the most important sources of information on the chemical composition of melts. This paper reports on the successful application of near-infrared (NIR) femtosecond laser ablation (LA) - inductively coupled plasma-mass spectrometry to in situ determination of incompatible trace elements (Li, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Ta, Th, U) and ore metals (As, Mo, Pb) in individual melt inclusions hosted in quartz from the Mount Pinatubo dacites, Philippines. The determined elements cover a concentration range of five orders of magnitude. Femtosecond LA-ICP-MS analyses of twenty-eight individual melt inclusions demonstrate the efficiency of the microanalytical technique and suggests a spectacular homogeneity of the entrapped melt, at least with respect to the following incompatible trace elements: Rb, Sr, Nb, Cs, Ba, La, Ce, Pr, Nd, Pb, Th. The analytical precision (1s) for Na, Ca, Rb, Sr, Y, Nb, Ba and LREE ranged from 3 to 20%. Comparison of trace element concentrations in Mt. Pinatubo melt inclusions determined by femtosecond LA-ICP-MS with those of melt inclusions previously analysed by secondary ion mass spectrometry analysis (SIMS) and those of matrix glasses previously determined by nanosecond LA-ICP-MS showed an agreement typically within 30–40%. The homogeneity of trace element concentrations of the Mt. Pinatubo melt inclusions and the matrix glasses is consistent with the melt inclusion origin as homogeneous rhyolitic melt that was trapped in quartz phenocrysts at the final crystallisation stages of the host adakite (dacite) magma.  相似文献   

16.
The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g-1 for Be and B and 200 ng g-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.  相似文献   

17.
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.  相似文献   

18.
Eclogite of recycled slab origin has often been invoked in the source region of mid-ocean ridge and ocean-island basalts. Melts of this eclogitic material are expected to be enriched in incompatible elements including major elements such as Na and Ti. In order to investigate the controls on trace element chemistry of a melt from such a recycled component we have performed trace element partitioning experiments in the simple systems CMAS (CaO-MgO-Al2O3-SiO2), NCMAS (Na2O-CMAS) and Ti-CMAS (TiO2-CMAS) at 3 GPa and 1298-1500°C using analogue eclogitic compositions.We show that sodium has a profound effect on clinopyroxene-melt partition coefficients. NCMAS is characterized by elevated partition coefficients, relative to CMAS for all elements except Li. The increase is more pronounced for more highly charged cations, resulting in negative partitioning anomalies for Li, Sr, Ba and Pb. In contrast to sodium, titanium has very little effect on trace element partitioning for all elements except Nb and Ta, which are retained by the rutile that is saturated in this run.  相似文献   

19.
Compact type A (CTA) inclusions are one of the major types of coarse-grained refractory inclusions found in carbonaceous chondrites. They have not been studied in a systematic fashion, leading to some uncertainties and unproven assumptions about their origin. To address this situation, we studied a total of eight CTAs from Allende, Efremovka and Axtell by scanning electron-microscopic and electron and ion-microprobe techniques. These inclusions are very melilite-rich, ranging from ∼60 vol% to nearly monomineralic. Also present are Mg–Al spinel (5–20%), perovskite (trace–∼3%) and, in some samples, Ti-rich (∼17 wt% TiO2tot) fassaite (trace–∼20%), and rhönite (≤1%). Melilite compositions are mostly between Åk15 and Åk40. Chondrite-normalized REE abundance patterns for melilite (flat at ∼10 × CI with positive Eu anomalies) and fassaite (slight HREE enrichment relative to LREE and negative Eu anomalies) are like those for their counterparts in once-molten type B inclusions. The patterns for rhönite have positive slopes from La through Lu and abundances <10 × CI for La and 35–60 × CI for Lu. Features of CTAs that suggest that they were once molten include: rounded inclusion shapes; positively correlated Sc and V abundances in fassaite; radially oriented melilite laths at inclusion rims; and the distribution of trace elements among the phases. Fractional crystallization models show that, with one exception, the REE contents of perovskite and fassaite arose by crystallization of these phases from late, residual liquids that would have resulted from prior crystallization of the observed proportions of melilite and spinel from liquids having the bulk compositions of the inclusions. One Allende CTA (TS32), however, has several features (irregular shape, reversely zoned melilite, fassaite REE contents) that are not readily explained by crystallization from a melt. This inclusion may have undergone little melting and may be dominated by relict grains.  相似文献   

20.
Eleven synthetic silicate and phosphate glasses were prepared to serve as reference materials for in situ microanalysis of clinopyroxenes, apatite and titanite, and other phosphate and titanite phases. Analytical results using different micro-analytical techniques showed that the glass fragments were homogeneous in major and trace elements down to the micrometre scale. Trace element determinations using inductively coupled plasma-mass spectrometry (ICP-MS), multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ionisation mass spectrometry (SIMS) showed good agreement for most elements (Li, Be, B, Cs, Rb, Ba, Sr, Ga, Pb, U, Th, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, Zr, Hf, Ta, Nb) studied and provide provisional recommended values.  相似文献   

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