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1.
The formation of phosphoran olivine by crystallization from a melt was investigated experimentally using a one atmosphere furnace, using San Carlos olivine [(Mg,Fe)2SiO4] mixed with either iron phosphide (FeP) or magnesium pyrophosphate (Mg2P2O7). Both dynamic crystallization and isothermal experiments produced phosphoran olivine as zoned single crystals and as overgrowths surrounding normal, phosphorus-free olivine grains. The crystallization pathways that form phosphoran olivine were traced and confirm that it is a metastable phase that can crystallize from a phosphorus-rich melt over timescales of hours to days. Removal of the P and equilibration of the olivine however requires weeks to months in the presence of silicate melt. Phosphoran olivine with up to 27 wt% P2O5 was generated and up to 69% of the Si tetrahedral sites were replaced by P. The substitution of Si by P into olivine was confirmed as 4VIM+2 + 2IVSi+4 ↔ 3VIM+2 + 2IVP+5 + VI[]. Phosphoran olivine compositions that vary from (Mg,Fe)2SiO4 to (Mg,Fe)1.65[]0.35Si0.3P0.7O4 have been produced in these experiments.Phosphoran pyroxene was also generated in a few experiments and forms when phosphoran olivine reacts with either tridymite or melt. It has compositions compatible with protopyroxene, orthopyroxene, pigeonite and sub-calcic augite, and can contain up to 31.5 wt% P2O5. Like phosphoran olivine, it is also a metastable phase. Phosphorus replaces Si in pyroxene by the following substitution methods: 8IVSi+4 ↔ 3IVSi+4 + 4IVP+5 + IV[] with Al entering the structure by the exchange 2IVSi+4 ↔ IVAl+3 + IVP+5. Phosphoran pyroxene compositions vary from (Mg,Fe)8Si8O24 to (Mg,Fe)8Si3P4[]O24.  相似文献   

2.
Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ7Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ7Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ7Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ7Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ7Li, the carbonatite and silicate melts produced remarkably contrasting δ7Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ7Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.  相似文献   

3.
Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ7Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ7Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ7Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ7Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ7Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.  相似文献   

4.
Major-, minor-, and trace-element zoning have been measuredin garnets from four samples of differing bulk composition fromthe east flank of the Shelburne Falls Dome, western Massachusetts,using ion and electron microprobes. The samples are differentiallyretrograded, so traditional techniques of rim geothermometryand geobarometry and P-T path analysis yield equivocal results. Trace-element abundances in garnets vary with those of majorelements, particularly calcium. Garnets exhibit several typesof Ca zoning, each accompanied by a distinct mode of trace-clementzoning. Garnets from low-Ca pelites in the Goshen Formationdecrease to low Ca abundances near their rims. This featureis coupled with a decrease in Na/Si and Ti/Si. The outermostfew microns of these garnets show a depletion in Sc/Si and anenrichment in Mn/Si, Y/Si, and rare earth element (REE) abundancescompared with the garnet core. These variations are ascribedto changes in intensive parameters during garnet growth/re-equilibration,probably a decrease in pressure (< 1 kb) accompanied by asmall temperature increase, which led to a decrease in XgrossularMuch of the variation in trace-element content may reflect crystal-chemicaleffects. In contrast, cores of garnets from intermediate-Capelites in the Waits River Formation initially display decreasesin grossular content, followed by Ca increases towards theirrims. The decrease in grossular content correlates with strongincreases in Y/Si, Zr/Si, and REE contents. The Ca ‘inflection’observed in these garnets coincides with the last appearanceof clinozoisite inclusions in garnet. Clinozoisite-compatibleelements (Y, Zr, and REE) may be released during breakdown ofclinozoisite in an internal metasomatic process, producing someof the trace-element enrichments. Garnets from clinozoisite-bearingpelites in the Waits River Formation exhibit zoning profileswith an increase in Ca towards the rim. An abrupt enrichmentin grossular content (Xgrossular = 0.06) occurs near garnetcores in these high-CaO, low-SiO2, high-FeO samples. The Caincrease accompanies small decreases in Li/Si and Na/Si, smallincreases in Ti/Si and V/Si, and large decreases in Y/Si, Zr/Si,and REE abundance. The large trace-element variations are probablydue to an interval of growth of clinozoisite accessory mineralsseparating two distinct garnet-growth events. This garnet alsoshows Co and Cr increases toward the rim, probably as a resultof breakdown of magnetite. Proton-probe microanalysis of minerals in these calc-pelitesshows strong affinities of specific trace elements for certainminerals: Y in garnet, Ga and Rb in biotite, Zn and Ga in staurolite,Rb and Sr in muscovite, Sr and Pb in plagioclase, and Nb inilmenite. Trace-element zoning is shown to be a useful monitor of reactionhistories and possibly P-T paths during garnet growth.  相似文献   

5.
The paper presents data on the composition of olivine macrocrysts from two Devonian kimberlite pipes in the Arkhangelsk diamond province: the Grib pipe (whose kimberlite belongs to type I) and Pionerskaya pipe (whose kimberlite is of type II, i.e., orangeite). The dominant olivine macrocrysts in kimberlites from the two pipes significantly differ in geochemical and isotopic parameters. Olivine macrocrysts in kimberlite from the Grib pipe are dominated by magnesian (Mg# = 0.92–0.93), Ti-poor (Ti < 70 ppm) olivine possessing low Ti/Na (0.05–0.23), Zr/Nb (0.28–0.80), and Zn/Cu (3–20) ratios and low Li concentrations (1.2–2.0 ppm), and the oxygen isotopic composition of this olivine δ18O = 5.64‰ is higher than that of olivine in mantle peridotites (δ18O = 5.18 ± 0.28‰). Olivine macrocrysts in kimberlite from the Pionerskaya pipe are dominated by varieties with broadly varying Mg# = 0.90–0.93, high Ti concentrations (100–300 ppm), high ratios Ti/Na (0.90–2.39), Zr/Nb (0.31–1.96), and Zn/Cu (12–56), elevated Li concentrations (1.9–3.4 ppm), and oxygen isotopic composition δ18O = 5.34‰ corresponding to that of olivine in mantle peridotites. The geochemical and isotopic traits of low-Ti olivine macrocrysts from the Grib pipe are interpreted as evidence that the olivine interacted with carbonate-rich melts/fluids. This conclusion is consistent with the geochemical parameters of model melt in equilibrium with the low-Ti olivine that are similar to those of deep carbonatite melts. Our calculations indicate that the variations in the δ18O of the olivine relative the “mantle range” (toward both higher and lower values) can be fairly significant: from 4 to 7‰ depending on the composition of the carbonate fluid. These variations were formed at interaction with carbonate fluid, whose δ18O values do not extend outside the range typical of mantle carbonates. The geochemical parameters of high-Ti olivine macrocrysts from the Grib pipe suggest that their origin was controlled by the silicate (water–silicate) component. This olivine is characterized by a zoned Ti distribution, with the configuration of this distribution between the cores of the crystals and their outer zones showing that the zoning of the cores and outer zones is independent and was produced during two episodes of reaction interaction between the olivine and melt/fluid. The younger episode (when the outer zone was formed) likely involved interaction with kimberlite melt. The transformation of the composition of the cores during the older episode may have been of metasomatic nature, as follows from the fact that the composition varies from grain to grain. The metasomatic episode most likely occurred shortly before the kimberlite melt was emplaced and was related to the partial melting of pyroxenite source material.  相似文献   

6.
Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ7Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ7Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ7Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ7Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ7Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ7Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ7Li), while non mantle-like, low δ7Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.  相似文献   

7.
Li isotope fractionation in peridotites and mafic melts   总被引：4，自引：0，他引：4  
We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of 7Li/6Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ7Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ7Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ7Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ7Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ7Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ7Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.  相似文献   

8.
Li behaviour and distribution in the mantle were investigated by ion microprobe in situ measurements on co-existing olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and amphibole (amp) in xenoliths from the French Massif Central. The fertile spinel lherzolites of this study record increasing degrees of mantle metasomatism, from unmetasomatised anhydrous samples through cryptically metasomatised samples to highly metasomatised amphibole-rich samples. In anhydrous lherzolites, Li is preferentially incorporated into olivine (1.1-1.4 ppm, average values) compared to pyroxenes (0.2-0.9 ppm). The hydrous samples clearly show enrichment of Li in ol (1.5-5.0 ppm), opx (1.1-2.4 ppm) and cpx (2.4-5.4 ppm), while amphibole incorporates less Li than the co-existing phases (0.8-1.3 ppm). Average δ7Li values range from +7.6 to +14.5‰ in ol, from 5.1 to +13.7‰ in opx and from 8.8 to +10.3‰ in cpx from the anhydrous lherzolites. A layered peridotite sample (Sdi) shows higher Li content in all phases, with lighter isotopic composition in opx and cpx (−0.6 and −2‰ average δ7Li values, respectively). In the hydrous lherzolites average δ7Li values both overlap and extend beyond these ranges in ol (up to 17.5 ‰) and in opx (up to 22.9‰), and vary widely in cpx (−2.7 to +9.7‰). Low δ7Li values are observed in some opx (−10.4‰) and cpx (−13‰) from sample Sdi, and in cpx from three hydrous samples (from −9.7 to −5.3‰). The different anhydrous phases from the hydrous samples show large intra-grain variations in Li isotopic ratios (e.g., up to 18‰) compared to the same phases from the anhydrous samples (mostly less than 6‰), excepting sample Sdi which has up to 20.4‰ variation in cpx. Similar to the anhydrous silicates, amphiboles show a wide variation of δ7Li values on the intra-grain scale (2-27‰). These variations are interpreted to result from fractionation processes during metasomatism by a silicate melt undergoing compositional changes as it percolates through and reacts with the peridotite phases. Thus Li abundances and isotopic in situ measurements are useful for tracing metasomatic processes but the heterogeneities observed in the samples preclude any identification of a specific mantle source by its Li signature.  相似文献   

9.
Titanium in phengite: a geobarometer for high temperature eclogites   总被引：1，自引：1，他引：0  
Phengite chemistry has been investigated in experiments on a natural SiO2–TiO2-saturated greywacke and a natural SiO2–TiO2–Al2SiO5-saturated pelite, at 1.5–8.0 GPa and 800–1,050°C. High Ti-contents (0.3–3.7 wt %), Ti-enrichment with temperature, and a strong inverse correlation of Ti-content with pressure are the important features of both experimental series. The changes in composition with pressure result from the Tschermak substitution (Si + R2+ = AlIV + AlVI) coupled with the substitution: AlVI + Si = Ti + AlIV. The latter exchange is best described using the end-member Ti-phengite (KMgTi[Si3Al]O10(OH)2, TiP). In the rutile-quartz/coesite saturated experiments, the aluminoceladonite component increases with pressure while the muscovite, paragonite and Ti-phengite components decrease. A thermodynamic model combining data obtained in this and previous experimental studies are derived to use the equilibrium MgCel + Rt = TiP + Cs/Qz as a thermobarometer in felsic and basic rocks. Phengite, rutile and quartz/coesite are common phases in HT-(U)HP metamorphic rocks, and are often preserved from regression by entrapment in zircon or garnet, thus providing an opportunity to determine the T–P conditions of crystallization of these rocks. Two applications on natural examples (Sulu belt and Kokchetav massif) are presented and discussed. This study demonstrates that Ti is a significant constituent of phengites that could have significant effects on phase relationships and melting rates with decreasing P or increasing T in the continental crust.  相似文献   

10.
The Montaña de Manganeso is a manganese vein-type deposit spatially associated with back-arc basin remnants of the Guerrero tectonostratigraphic terrane. The study of major- and trace-element geochemical characteristics of the deposit provides insight into the controls on ore-forming processes within the area. The deposit is characterized by low Co, Cu and Ni abundances, and high Ba (>10,000 ppm) contents and Mn/Fe ratios (<500), typical of hydrothermal Mn deposits. In addition, the low ∑REE abundances (18.7 to 103 ppm), negative Ce anomalies (0.2 to 0.6), and positive Y (1.00 to 2.34) and Eu anomalies (0.6 to 4.4) also suggest a hydrothermal source for the deposit. Discrimination plots involving ∑REE and Zr vs. (Cu + Ni + Co) and Ce/Ce* vs. Nd and Y/Ho further indicate a hydrothermal source in an oxidizing depositional environment. The Mn-Fe-(Ni + Cu + Co), MnO2-MgO-Fe2O3, (Cu/Zn)/Fe2O3 vs. (Zn/Ni)/MnO2 and Na/Mg diagrams display intermediate signatures between marine and terrestrial environments. This suggest that the Montaña de Manganeso deposit is the result of two metallogenic stages: (I) the earliest stage, which involved the formation of Mn oxides by hydrothermal/diagenetic processes in the Arperos back-arc basin during the Cretaceous; and (II) the latest stage took place subsequent to accretion the Guerrero tectonostratigraphic terrane onto the continent and involved the remobilization of the Cretaceous submarine Mn oxides (and associated trace elements) and subsequent redepositation by Tertiary continental hydrothermal activity.  相似文献   

11.
 Si K- and L-edge ELNES spectroscopy and multiple-scattering (MS) calculations are used to examine mixed Si coordination compounds varying in SiVI:SiIV ratio. As in previous studies, the edges are influenced mainly by silicon coordination (tetrahedral vs. octahedral), as supported by the MS calculations. We demonstrate two methods semi-quantitatively to extract the value of SiVI/(SiVI+SiIV): (1) A linear relationship between the L2,3-L1 splitting and SiVI/(SiVI+SiIV) is observed, (2) a fitting method based on the coaddition of reference tetrahedral and octahedral Si spectra is applied to both Si K- and L-edge ELNES spectra. Received: February 10, 1997 / Revised, accepted: May 23, 1997  相似文献   

12.
Compositional variation (results of electron microprobe analyses and mass-spectrometry analyses) of columbite-group minerals (CGM) from fully differentiated albite–spodumene pegmatites at Kolmozero in the Kola Peninsula is evaluated. Concentric zoning, typical of rare-metal pegmatites, was not observed in the Kolmozero pegmatites. Columbite-group minerals occur in all main parageneses of the pegmatites and form four generations, reflecting the sequence of pegmatite formation. These minerals demonstrate wide variations in the content of major and trace elements. The composition of CGM ranges from columbite-(Fe) to tantalite-(Mn). Fractionation trends were observed in Mn/(Mn + Fe) versus Ta/(Ta + Nb) diagrams and trace-element abundances plotted versus XTa and XMn. The early CGM paragenesis is characterized by homogeneous, oscillatory and progressive oscillatory zoning and corresponds to a primary magmatic type. Late-generation CGM show patchy irregular internal textures replacing earlier regular patterns of zoning. The irregular zoning points to metasomatic replacement processes. For the first time, it is shown that distributions of rare earth elements (REE) in CGM reflect the evolution of a pegmatite-forming system. At Kolmozero, the main trend of REE variation from early to late generations of CGM involves decreasing total REE contents due to a decrease in heavy REE and Y, decreasing negative Eu anomaly and decreasing magnitude of M-shape tetrad effect between Gd and Ho. These changes are accompanied by gradual flattening of the “bird-like” patterns of chondrite-normalized REE distribution. All these features are typical for late differentiates of granitic volatile-rich magma. Late metasomatic tantalite-(Mn) is characterized by sharp changes in its REE distribution pattern: decreasing total REE contents, changing shape of the REE distribution pattern, the absence of Eu anomaly and tetrad effects, and the appearance of a negative Ce anomaly. The textural characteristics and mineral chemistry of CGM indicate that the pegmatite-forming system underwent several stages of evolution. The earliest magmatic stage can be divided into two sub-stages, involving direct crystallization and collective recrystallization, respectively, and was succeeded by a late hydrothermal–metasomatic post-magmatic stage. Variations in chemical composition among the different generations of CGM are explained by the interplay of several processes: fractional crystallization; competitive crystallization of main rock-forming (feldspar, muscovite, spodumene) and accessory (triphylyte–lithiophilite, spessartine, fluorapatite, zircon, microlite) minerals; and evolution of the mineral-forming environment from a melt to a hydrothermal–metasomatic fluid.  相似文献   

13.
Ion-microprobe was used to measure Li abundances and isotopic compositions in pyroxenes from three Martian meteorites belonging to the nakhlite family. The profiles performed across augite crystals from Northwest Africa 817 show a large isotopic zoning from crystal cores (δ7Li ∼ 0‰) to rims (δ7Li ∼ +20‰) while Li abundances are almost constant (∼9.2 μg/g). Unlike NWA 817, the pyroxene studied in the Miller Range 03346 nakhlite shows a zoning in Li abundance, with concentrations increasing from ∼2.5 μg/g in the core to ∼9 μg/g in the rim. The augite rim (δ7Li = +7‰) is slightly enriched in 7Li with regard to the core (δ7Li = +4‰), but most of the isotopic variations observed occur at an intermediate position along the profile, where δ7Li falls down to ∼−11‰. In the case of Nakhla, Li concentrations in augite increase from cores (∼3.5 μg/g) to rims (∼6.5 μg/g), while the δ7Li variation is restricted (i.e., between δ7Li = +6.0 and +12.6‰). For the three meteorites the Li abundances were also measured in the groundmass, which was found to be enriched in lithium (∼10 μg/g). Conventional magmatic and post-magmatic processes such as alteration and fractional crystallization, fail to explain the dataset obtained on nakhlites. Degassing processes, which were previously proposed to explain the Li distribution in shergottite crystals, cannot result in the strong decoupling between Li abundances and isotopic composition observed in nakhlites. We suggest that the original magmatic Li distributions (concentrations and isotopic compositions) in nakhlites have been modified by diffusion of Li from the Li-rich groundmass towards the pyroxene crystals during sub-solidus cooling. Diffusion appears to have been efficient for NWA 817 and MIL 03346 but, apparently, did not produce a significant migration of Li in Nakhla, possibly because of the lower abundance of groundmass in the latter. Diffusion induced Li redistributions may also affect terrestrial porphyric rocks but very specific cooling rates are required to quench the diffusion profiles as observed in two of the present nakhlites.  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.
Mg-Al-rich rocks from the Palghat-Cauvery Shear Zone System (PCSZ) within the Gondwana suture zone in southern India contain sodicgedrite as one of the prograde to peak phases, stable during T = 900–990°C ultrahigh-temperature metamorphism. Gedrite in these samples is Mg-rich (Mg/[Fe + Mg] = X Mg = 0.69–0.80) and shows wide variation in Na2O content (1.4–2.3 wt.%, NaA = 0.33–0.61 pfu). Gedrite adjacent to kyanite pseudomorph is in part mantled by garnet and cordierite. The gedrite proximal to garnet shows an increase in NaA and AlIV from the core (NaA = 0.40–0.51 pfu, AlIV = 1.6–1.9 pfu) to the rim (NaA = 0.49–0.61 pfu, AlIV = 2.0–2.2 pfu), suggesting the progress of the following dehydration reaction: Ged + Ky → Na-Ged + Grt + Crd + H2O. This reaction suggests that, as the reactants broke down during the prograde stage, the remaining gedrite became enriched in Na to form sodicgedrite, which is regarded as a unique feature of high-grade rocks with Mg-Al-rich and K–Si-poor bulk chemistry. We carried out high-P-T experimental studies on natural sodicgedrite and the results indicate that gedrite and melt are stable phases at 12 kbar and 1,000°C. However, the product gedrite is Na-poor with only <0.13 wt.% Na2O (NaA = 0.015–0.034 pfu). In contrast, the matrix glass contains up to 8.5 wt.% Na2O, suggesting that, with the progressive melting of the starting material, Na was partitioned into the melt rather than gedrite. The results therefore imply that the occurrence of sodicgedrite in the UHT rocks of the PCSZ is probably due to the low H2O activity during peak P-T conditions that restricted extensive partial melting in these rocks, leaving Na partitioned into the solid phase (gedrite). The occurrence of abundant primary CO2-rich fluid inclusions in this rock, which possibly infiltrated along the collisional suture during the final amalgamation of the Gondwana supercontinent, strengthens the inference of low water activity.  相似文献   

16.
During convergence of Gondwana-derived microplates and Laurussia in the Palaeozoic, subduction of oceanic and continental crusts and their sedimentary cover introduced material of regionally contrasting chemical and isotopic compositions into the mantle. This slab material metasomatised the local mantle, producing a highly heterogeneous lithospheric mantle beneath the European Variscides. The eastern termination of the European Variscides (Moldanubian and Saxo-Thuringian zones of Austria, Czech Republic, Germany and Poland) is unusual in that the mantle was modified by material from several subduction zones within a small area. Orogenic lamproites sampled this lithospheric mantle, which has a chemical signature reflecting extreme depletion (low CaO and Al2O3 contents and high Mg-number) followed by strong metasomatic enrichment, giving rise to crust-like trace element patterns, variable radiogenic 87Sr/86Sr(330) (0.7062–0.7127) and non-radiogenic Nd isotopic compositions (εNd(330) = − 2.8 to − 7.8), crustal Pb isotopic compositions, and a wide range of δ7Li values (− 5.1 to + 5.1). This metasomatic signature is variably expressed in the lamproites, depending on the extent of melting and the nature of the source of the metasomatic component. Preferential melting of the metasomatically enriched (veined) lithospheric mantle with K-rich amphibole resulted in lamproitic melts with very negative, crust-like δ7Li values, which correlate positively with peralkalinity, HFSE contents and lower εNd. Both the higher degree of melting and progressive consumption of the metasomatic component reduce the chemical and isotopic imprints of the metasomatic end member. The very positive δ7Li values of some lamproites indicate that the source of these lamproites may have been modified by subducted oceanic lithosphere. Fresh olivine from the Brloh (Moldanubian) lamproitic dyke shows very high Fo (up to 94%) and very high Li contents (up to 25 ppm), demonstrating that the extremely depleted and later enriched lithospheric mantle may have contributed significantly to the Li budget of the lamproites. The regional distribution of lamproites with contrasting chemical and isotopic fingerprints mimics the distribution of the different Variscan subduction zones.  相似文献   

17.
Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (expandable chlorite) and/or have excess AlVI relative to AlIV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and expandable chlorite, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high AlVI/AlIV and low FeVI/(Fe+Mg)VI ratios of chlorites are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low AlIV/SiIV and low FeVI/(Fe+Mg)VI, while chlorite has high AlIV/SiIV and high FeVI/(Fe+Mg)VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower AlIV/SiIV and FeVI/(Fe+Mg)VI. The ratios of FeVI/(Fe+Mg)VI and AlIV/SiIV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of chlorites in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.  相似文献   

18.
Feng Guo  Weiming Fan  Ming Zhang 《Lithos》2004,78(3):291-305
K-Ar dating, major- and trace-element and Sr-Nd isotopic analyses were carried out for early Cretaceous (122-127 Ma) lamprophyres from the Sulu orogen in eastern China. The results show strong fractionation in rare-earth elements with (LREE) >100 times chondrite, but HREE <10 times chondrite, indicating the presence of residual garnet in the melting source. These rocks are characterized by significant LILE and LREE enrichment but Nb and Ta depletion with moderate Zr/Hf (39.8-50.8 with regard to 36 for primitive mantle) and Nb/Ta (17.8-23.0, compared with 17.5 for primitive mantle) fractionations, probably as a consequence of carbonate- and rutile-rich melt metasomatism induced by dehydration and/or melting of subducted continental slab at mantle depths. Age-correlated Sr-Nd isotope ratios show moderate ranges of 87Sr/86Sr(i) from 0.70787 to 0.70934 and −17.2 to −11.6 of εNd(t). The lamprophyres from the Sulu orogen were derived from decompression melting of such a metasomatized lithospheric mantle that was mainly composed of phlogophite garnet peridotites and experienced crystal fractionation of a mineral assemblage of olivine+clinopyroxene±plagioclase en route to the surface. Such geochemical and isotopic signatures are also prevalent in the contemporaneous basaltic lavas in the Dabie-Sulu belt, suggesting predominant enrichment processes by carbonate- and rutile-rich metasomatic assemblage beneath the continental collisional belt.  相似文献   

19.

The Miocene lamproites of the West Kimberley region, Western Australia include olivine-leucite lamproites (≤10 wt% MgO) containing olivine and leucite microphenocrysts, and diamondiferous olivine lamproites (20–30 wt% MgO) containing olivine phenocrysts and larger (1–10 mm) olivine as mantle xenocrysts and dunite micro-xenoliths. Olivine phenocrysts and thin (<100 μm) magmatic rims define trends of decreasing Cr and Ni, and increasing Ca and Mn, with decreasing olivine Mg#, consistent with fractional crystallisation of olivine (and minor chromite). Many phenocrysts are zoned, and those with cores of similar Mg# and trace element abundances to the mantle xenocrysts may be xenocrysts overgrown by later olivine crystallised from the lamproite magma. Magmatic olivines Mg#91–92 are estimated to have been in equilibrium with olivine lamproite magma(s) containing ~22–24 wt% MgO. The xenocrystic mantle olivines Mg90–92.5 in the olivine lamproites are inferred from trace element abundances to be mostly derived from garnet peridotite with equilibration temperatures estimated from the Al-in-olivine thermometer (Bussweiler et al. 2017) to be ~1000–1270 °C at depths of 115–190 km. Olivines from the deeper lithosphere are less depleted (lower Mg#, higher Na, Al, P, Ti, Zr etc) than those at shallower depths, a feature suggested to reflect the combined effects of metasomatic re-enrichment of the craton roots (Ti, Fe, Zr etc) and increasing temperature with depth of origin (Na, Al, Ca). The West Kimberley lamproite olivines are not enriched in Li, as might be expected if their source regions contained continental sedimentary material as has been previously inferred from lamproite large-ion-lithophile trace elements, and Sr and Pb isotopes.

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20.
In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ56Fewr = 0.06–0.17‰ and δ7Lima = 2.5–5.2‰, assuming δ7Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ56Feol = ? 0.24 to 0.14‰ and δ7Liol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ56Feol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ7Licpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ7Liol-melt = ? 13; Δ56Feol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ7Liol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Liol/Limelt), indicating Li isotope fractionation due to preferential (faster) diffusion of 6Li into olivine during fractional crystallization. Olivine with low Δ7Liol-melt, also have low Δ56Feol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ56Feol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ56Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe3 +/Fe2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.  相似文献   

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