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1.
The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46Ti48Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. We provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components. The absolute Ti and Ca isotopic compositions still support the correlation of 50Ti and 48Ca effects in the FUN inclusions and imply contributions from neutron-rich equilibrium or quasi-equilibrium nucleosynthesis. The present identification of endemic effects at 46Ti, for the absolute composition, implies a shortfall of an explosive-oxygen component or reflects significant isotope fractionation. Additional nucleosynthetic components are required by 47Ti and 49Ti effects. Components are also defined in which 48Ti is enhanced.Bulk samples of carbonaceous meteorites (C2 and C3 types) show distinct excesses at 50Ti but no nonlinear effects at the other Ti isotopes. Other chondrites, including Orgueil (Cl), show no nonlinear effects. Relative to terrestrial Ti, a small isotope fractionation is found for only an enstatite chondrite. The Ti absolute compositions in Ca-Al-rich inclusions show significant isotope fractionation effects corresponding to an enhancement in the heavier isotopes relative to the lighter isotopes as compared to Ti in a TiO2 standard and in chondrites. The absence of a correlation of Ti isotope fractionation effects with those for Ca and Mg is indicative of multiple processes of condensation, volatilization and recondensation; however, the mechanisms causing the isotope fractionation are not well understood.  相似文献   

2.
We report measurements of the absolute isotope abundance of Ca in Ca-Al-rich inclusions from the Allende and Leoville meteorites. Improved high precision measurements are reported also for 46Ca. We find that nonlinear isotope effects in Ca are extremely rare in these inclusions. The absence of nonlinear effects in Ca, except for the effects in FUN inclusions, is in sharp contrast to the endemic effects in Ti. One fine-grained inclusion shows an excess of 46Ca of (7 ± 1)%., which is consistent with addition of only 46Ca or of an exotic (1) component with 46Ca1 ~ 48Ca1. FUN inclusion EK-1-4-1 shows a small 46Ca excess of (3.3 ± 1.0)%.; this confirms that the exotic Ca components in EK-1-4-1 were even more deficient in 46Ca relative to 48Ca than is the case for normal Ca. The Ca in the Ca-Al-rich inclusions shows mass dependent isotope fractionation effects (as deduced from the absolute 40Ca44Ca) which have a range from ?3.8 to +6.7%. per mass unit difference. This range is a factor of 20 wider than the range previously established for bulk meteorites and for terrestrial and lunar samples. Ca and Mg isotope fractionation effects in the Ca-Al-rich inclusions are common and attributed to kinetic isotope effects which imply the production of the inclusions by complex sequences of condensation, vaporization and recondensation. A correlation was found between Ca and Mg isotope fractionation effects and inclusion type. A possible correlation between isotope fractionation and rare earth element abundance patterns is discussed.  相似文献   

3.
4.
The solubility of rutile has been determined in a series of compositions in the K2O-Al2O3-SiO2 system (K1 = K2O(K2O + Al2O3) = 0.38–0.90), and the CaO-Al2O3-SiO2 system (C1 = CaO(CaO + Al2O3) = 0.47–0.59). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the K1 ratio. For example, at 1475°C the amount of TiO2 required for rutile saturation varies from 9.5 wt% (K1 = 0.38) to 11.5 wt% (K1 = 0.48) to 41.2 wt% (K1 = 0.90). In the CAS system at 1475°C, rutile solubility is not a strong function of C1. The amount of TiO2 required for saturation varies from 14 wt% (C1 = 0.48) to 16.2 wt% (C1 = 0.59).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K+ in excess of that needed to charge balance Al3+. The suggested stoichiometry of this complex is K2Ti2O5 or K2Ti3O7. In CAS melts, the data suggest that Ca2+ in excess of A13+ is not as effective at complexing with Ti as is K+. The greater solubility of rutile in CAS melts when C1 is less than 0.54 compared to KAS melts of equal K1 ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiKβ x-ray emission spectra of KAS glasses (K1 = 0.43–0.60) with 7 mole% added TiO2, rutile, and Ba2TiO4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba2TiO4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.  相似文献   

5.
The U-Th-Pb isotope systematics of the eucrite “Juvinas” have been studied in whole rock fragments as well as in plagioclases and pyroxenes. The results show that this monomict breccia crystallized with a very high UPb initial ratio at T = 4.539 ± 0.004 AE ago. There is evidence for a less radiogenic Pb component (206Pb204Pb = 13.0; 207Pb204Pb = 13.5; 208Pb204Pb = 32.71) interpreted as “exotic lead” induced by a meteoritical impact at the surface of the Juvinas parent body, 1.92 ± 0.06 AE ago.  相似文献   

6.
The ion microprobe was used to measure Ti and Mg isotopes as well as rare earth and other trace elements in ten hibonites from the CM carbonaceous chondrites Murchison, Murray, and Cold Bokkeveld and in two hibonites and Ti-rich pyroxene from the CV chondrite Allende. In hibonites from Murchison and Murray fission track densities were also measured, as were Th and U concentrations. Eight of the hibonites, from all four meteorites, exhibit large Ti isotopic anomalies, particularly in 50Ti. Two grains from Murray have 50Ti excesses of ~ 10%. At least four nucleosynthetic components are required to account for all the Ti isotopic data. Neutron-rich nuclear statistical equilibrium nucleosynthesis is the most likely process to account for a 50Ti-rich component (with 50Ti49Ti$̆20). The ion probe Ti isotopic measurements confirm that the solar nebula was isotopically heterogeneous on a small spatial scale and argue for a chemical memory origin of the Ti isotopic anomalies which were probably carried into the solar system in the form of refractory dust grains. However, there is no experimental evidence that such interstellar grains survived the formation of the hibonites. The REE and trace element patterns of the hibonites are similar to those seen in CAIs and can be interpreted in terms of fractionation effects during condensation from a gas of solar composition, thus arguing for a solar system origin of the hibonites. Additional evidence for such an origin is provided by the PuTh ratios, which are ~ 10−4, and by the Mg isotopic compositions which are normal except for 26Mg1 due to 26Al.Only three out of ten hibonites exhibit 26Mg1, consistent with previous studies which demonstrated the paucity of 26Mg1 in hibonites. Because of the refractory nature of hibonite and the presence of large Ti isotopic effects, we conclude that a heterogeneous distribution of 26Al in the early solar system is the most likely reason. In particular, our observations of δ50Ti = 15%. and of an isochron with (26Al27Al)0 = 5 × 10−8 in the FUN inclusion HAL are evidence against both late formation and Mg redistribution to explain the lack of 26Al in hibonites.There are no obvious correlations between the Ti isotopic compositions, the presence of 26Mg1, the presence of 244Pu, and the REE and trace element patterns in individual hibonites. This indicates that the anomalous 50Ti, as well as 26A1 and 244Pu, were not co-produced in a single astrophysical source, and/or that these nuclides were introduced into the solar nebula by different carriers before being incorporated into the hibonites.  相似文献   

7.
High precision mass spectrometric determination of calcium isotope ratios allows the 40K → 40Ca radioactive decay to be used for dating a much broader range of geologic materials than is suggested by previous work. 40Ca42Ca is used to monitor enrichments in 40Ca and can be measured to ±0.01% (2σ) using an exponential mass discrimination correction (Russell et al., 1978) and large ion currents. The earth's mantle has such a low KCa (~0.01) that it has retained “primordial” 40Ca42Ca = 151.016 ± 0.011 (normalized to 42Ca44Ca = 0.31221), as determined by measurements on two meteorites, pyroxene from an ultramafic nodule, metabasalt, and carbonatite. 40Ca42Ca ratios can be conveniently expressed relative to this value as ?Ca in units of 10?4. To test the method for age dating, a mineral isochron has been obtained on a sample of Pikes Peak granite, which has been shown to have concordant KAr, RbSr, and UPb ages. Plagioclase, K-feldspar, biotite, and whole rock yield an age of 1041 ± 32 m.y. (2σ) in agreement with previous age determinations (λK = 0.5543 b.y.?1, λβ?λK = 0.8952, 40K = 0.01167%). The initial 40Ca42Ca of 151.024 ± 0.016 (?Ca = +0.5 ± 1.0), indicates that assimilation of high K/Ca crust was insufficient to affect calcium isotopes. Measurements on two-mica granite from eastern Nevada indicate that the magma sources had K/Ca ≈ 1, similar to intermediate-composition crustal rocks. These results show that the KCa system can be used as a precise geochromometer for common felsic igneous and metamorphic rocks, and may prove applicable to sedimentary rocks containing authigenic K minerals. The relatively short half-life of 40K, the non-volatile daughter, and the fact that potassium and calcium are stoichiometric constituents of many minerals, make the KCa system complementary to other dating methods, and potentially applicable to a variety of geologic problems.  相似文献   

8.
We present Ca isotopic measurements on Allende Ca-Al-rich inclusions (CAIs) and an apatite enriched fraction from Orgueil. The results on CAIs show widespread excesses on the neutron-rich isotope 48Ca. All other isotopes agree with the normal within our presently obtainable precision. Seven out of 11 CAIs analyzed exhibit isotopic anomalies ranging up to ~ +6? units (1? = 1 part in 10,000). This abundant occurrence of isotopic excesses places Ca alongside Ti and O, elements which show isotopic anomalies in all Allende CAIs measured so far. However, at present no clear correlation can be found between excesses in 48Ca and 50Ti, the isotopes which are thought to be coproduced by neutron-rich nucleosynthetic processes within stars. We believe that the relatively higher volatility of Ca compared to Ti compounds could have led to a variable dilution with isotopically “normal” Ca in vaporization and recondensation processes in stellar envelopes, the interstellar medium and/or the solar nebula. High precision measurements of 46Ca limit possible anomalies in this 33 ppm abundance isotope to 10? units or less and, together with the observed 48Ca and 50Ti anomalies, constrain possible nucleosynthetic mechanisms capable of producing these neutron-rich nuclei.  相似文献   

9.
10.
The concentrations of noble gas isotopes of He, Ne and Ar have been measured in eight mineral separates of the Bruderheim chondrite. The cosmic-ray-produced nuclides 21Ne and 38Ar were correlated by a computer least-squares fitting program with the elemental composition in each separate of potential targets for nuclear production yielding the following production equations: [21Ne, 10?8 cm3/g] = k(0.45[Mg] + 0.085[Si] + 0.060[S] + 0.017[Ca] + 0.0044[Fe + Ni]); [38Ar, 10?8 cm3/g] = k(2.6[K] + 0.37[Ca] + 0.08[Ti + Cr + Mn] + 0.021[Fe + Ni]) with elemental concentrations in weight per cent and k equal to the reciprocal of the cosmic-ray exposure age of Bruderheim. The P(S)/P(Cr + Mn + Fe + Ni) weight production ratio for 3He was determined to be 1.53; relative productions of 3He from O, Mg and Si and 21Ne from Al proved to be incalculable.  相似文献   

11.
18O16O, 13C12C and 87Sr86Sr ratios have been measured on the same samples for carbonatite complexes. The results show that besides the ‘carbonatite box’ of Tayloret al. (1967) there exist higher δ18O and δ13C values than can be explained by late magmatic or deuteric processes. These processes correspond to high concentrations of CO2 and lead to big enrichments in 18O and 13C as well as in some ‘volatile’ elements. Strontium results are consistent with a model of selective contamination of deep-seated material by highly radiogenic strontium. The whole study leads to the opinion that parent magmas of carbonatites differentiated in a crustal environment with or without significant contamination.  相似文献   

12.
J.G Rønsbo  A.K Pedersen  J Engell 《Lithos》1977,10(3):193-204
Microprobe analyses on a xenocrystic suite of salites, aegirine-augites, aegirines, titan-aegirines and acmites from a lower Tertiary ash layer in northern Denmark are presented. The sodic pyroxenes show an unusual titan-enrichment and up to 42 mol.% of the component NaTi124+M122+Si3O6 (M = Fe2+, Mn or Mg), is estimated. Optical absorption measurements show no evidence for Ti3+. The titan-aegirines were formed during late to post-magmatic crystallization in a system with a high Ti4+/Fe2+ ratio and were followed by acmite showing enrichment in jadeite. Comparison with experimentally investigated titan-aegirine indicates crystallization far below the Mn2O3Mn3O4f02 buffer.  相似文献   

13.
The 176Lu-176Hf isotope method and its applications in earth sciences are discussed. Greater fractionation of Lu/Hf than Sm/Nd in planetary magmatic processes makes 176Hf177Hf a powerful geochemical tracer. In general, proportional variations of 176Hf177Hf exceed those of 143Ndl44Nd by factors of 1.5–3 in terrestrial and lunar materials. Lu-Hf studies therefore have a major contribution to make in understanding of terrestrial and other planetary evolution through time, and this is the principal importance of Lu-Hf. New data on basalts from oceanic islands show unequivocally that whereas considerable divergences occur in 176Hf177Hf-87Sr86Sr and 143Ndl44Nd-87Sr86Sr diagrams, 176Hf177Hf and 143Nd144Nd display a single, linear isotopic variation in the suboceanic mantle. These discordant 87Sr86Sr relationships may allow, with the acquisition of further Hf-Nd-Sr isotopic data, a distinction between processes such as mantle metasomatism, influence of seawater-altered material in the magma source, or recycling of sediments into the mantle. In order to evaluate the Hf-Nd isotopic correlation in terms of mantle fractionation history, there is a need for measurements of Hf distribution coefficients between silicate minerals and liquids, and specifically for a knowledge of Hf behavior in relation to rareearth elements. For studying ancient terrestrial Hf isotopic variations, the best quality Hf isotope data are obtained from granitoid rocks or zircons. New data show that very U-Pb discordant zircons may have upwardly-biased 176Hf177Hf, but that at least concordant to slightly discordant zircons appear to be reliable carriers of initial 176Hf177Hf. Until the controls on addition of radiogenic Hf to zircon are understood, combined zircon-whole rock studies are recommended. Lu-Hf has been demonstrated as a viable tool for dating of ancient terrestrial and extraterrestrial samples, but because it offers little advantage over existing methods, is unlikely to find wide application in pure chronological studies.  相似文献   

14.
The synthetic chelating agent ethylenediaminetetraacetic acid (EDTA) has been used to evaluate the stoichiometric solubility product of galena (PbS) at 298°K: Ks2 = aPb2+aHS?aH+ This method circumvents the possible uncertainties in the stoichiometry and stability of lead sulfide complexes. At infinite dilution, Log Ks2 = ?12.25 ±0.17, and at an ionic strength corresponding to seawater (I = 0.7 M), Log Ks2 = ?11.73 ± 0.05. Using the value of Ks2 at infinite dilution, and the free energies of formation of HS? and Pb2+ at 298°K (literature values), the free energy of formation of PbS at 298°K is computed to be ?79.1 ± 0.8 KJ/mol (?18.9 Kcal/mol). Galena is shown to be more than two orders of magnitude more soluble than indicated by calculations based on previous thermodynamic data.  相似文献   

15.
The decay constant 87Rb has been redetermined by measuring the amount of radiogenic 87Sr produced over a period of 19 years, in 20 g samples of purified RbClO4, using isotope dilution techniques. The rubidium sample was spiked with 84Sr and the nanogram quantities of strontium separated by coprecipitation with Ba(NO3)2. Analyses were carried out on a 25cm, 90° sector mass spectrometer equipped with a Spiraltron electron multiplier. Measurement of three independent ratios permitted continuous monitoring of the ion beam fractionation. The average of nine determinations gives a value for the decay constant of 1.419(±0.012) × 10?11 yr?1 (2σ). [τ12 = 4.89(±0.04) × 1010yr.]  相似文献   

16.
The South Mountain batholith of southwestern Nova Scotia is a large, peraluminous, granodiorite-granite complex which intrudes mainly greenschist facies metasediments of the Cambro-Ordovician Meguma Group. Using Rb-Sr isochrons constructed from whole rocks and mineral separates, the present study shows a variation in age and initial ratios of the intrusive phases of the batholith as follows: biotite granodiorite (371.8 ± 2.2 Ma, (87Sr86Sr)i ranges from 0.7076 ± 0.0003 to 0.7090 ± 0.0003, with the average = 0.7081); adamellite (364.3 ± 1.3 Ma, (87Sr86Sr)i = 0.70942 ± 35); porphyry (361.2 ± 1.4 Ma, (87Sr86Sr)i = 0.71021 ± 119); using λ87Rb = 1.42 × 10?11yr?1.A suite of Meguma country rock samples showed a variation of 87Sr86Sr = 0.7113?0.7177 at the time of intrusion of the batholith. A number of xenoliths of this material occurring in the marginal granodiorite had partially equilibrated isotopically with the granodiorite at a higher 87Sr86Sr ratio than elsewhere in the granodiorites. This evidence demonstrates that isotopic (and probably some accompanying bulk chemical) contamination by the Meguma rocks has been an important factor in determining the ultimate chemical composition and mineralogy of the South Mountain batholith.The (87Sr86Sr)372 = 0.7081 of the early granodiorites indicates that the parent magma of the South Mountain batholith was derived from a source unlike the Meguma Group. The precise nature of the source region cannot be determined by Rb-Sr work unless the degree of contamination with Megumalike material is known.  相似文献   

17.
Differences in the chemical composition of metamorphic and igneous pyroxene minerals may be attributed to a transfer reaction, which determines the Ca content of the minerals, and an exchange reaction, which determines the relative Mg:Fe2+ ratios. Natural data for associated Ca pyroxene (Cpx) and orthopyroxene (Opx) or pigeonite are combined with experimental data for Fe-free pyroxenes, to produce the following equations for the Cpx slope of the solvus surface: > 1080°C: T = 1000(0.468 + 0.246XCpx ? 0.123 ln (1–2 [Ca]))< 1080°C: T = 1000(0.054 + 0.608XCpx ? 0.304 ln (1–2 [Ca])), and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: T = 1130(ln Kp + 0.505), where T is absolute temperature, X is Fe2+(Mg + Fe2+)), [Ca] is Ca(Ca + Mg + Fe2+) in Cpx, and KD is the distribution coefficient, defined as XOpx/(1 ? XOpx) ÷ XCpx/(1 ? Cpx).The transfer and exchange equations form useful temperature indicators, and when applied to 9 sets of well-studied rocks, yield pairs of temperatures that are in good agreement. For example, temperatures obtained for the Bushveld Complex are 1020°C (solvus equation) and 980°C (exchange equation), based on 7 specimens. The uncertainty in these numbers, due to precision and accuracy errors, is estimated to be ±60°.  相似文献   

18.
The isotopic composition of strontium of pore water and of authigenic minerals leached from the sediment of core 119K with hot aqua regia is similar to that of the brine in the Discovery deep and differs from that of normal seawater. The average 87Sr86Sr ratio of strontium removed by acid leaching is 0.7077 ± 0.0007 (1σ) compared to a value of 0.70904 for the Red Sea. The detrital silicate fraction exhibits an approximate inverse correlation between 87Sr86Sr ratios and strontium concentrations which provides tentative support for a model in which the detrital silicate fraction of deep-sea sediment is considered to be a mixture of terrigenous dust of sialic composition enriched in radiogenic 87Sr and of volcanogenic material of basaltic composition and low 87Sr abundance. The 87Sr86Sr ratios of the shells of foraminifers and pteropods, expressed as δ 87Sr‰ relative to 0.70904 for seawater, decrease from ?0.23 ± 0.17‰ at 90 cm to ?0.82 ± 0.17‰ at 273 cm and remain constant at this value to a depth of 450 cm. The lowering of the δ 87Sr values is attributed both to the presence of aragonite overgrowths on pteropod shells and to possible isotope exchange with strontium in the connate fluid.  相似文献   

19.
20.
To better understand the process of crustal contamination/assimilation, 23 Pb isotopic compositions and 12 concentrations have been measured on lavas and basement rocks from the Edgecumbe volcanic field, SE Alaska. Measured isotopic ratios have the following ranges: 206Pb204Pb = 18.477–19.161; 207Pb204Pb = 15.562–15.679; 208Pb204Pb = 38.17–38.85. While the data form well-constrained linear arrays on Pb-Pb diagrams, no simple correlation exists with major element composition. Basaltic lavas (≤ 51 wt% SiO2) are characterized by two isotopic groups. The olivine basalt (≤ 48% SiO2) is more radiogenic than the plagioclase basalt (48–51%) which also shows more heterogeneity. In the silica range 52–55%, Pb isotopic ratios increase significantly but remain fairly constant in the range 55–70% SiO2. Lead concentrations vary from 1 ppm in the basalts to 7 ppm in the rhyodacites. Analyzed basement rocks are more radiogenic than any of the lavas (206Pb204Pb = 19.20; 207Pb204Pb = 15.65; 208Pb204Pb = 38.86. The Pb isotopic data are qualitatively consistent with the contamination process described by Myerset al. (1984). However, because of fundamental differences in the mixing relations between the Sr system studied earlier and the Pb system, the new Pb data have revealed details of the process not apparent from the Sr data alone. In particular, it has been shown that the parent magma was more primitive than originally assumed, and that two contamination events are recorded in the lavas. The first event, involving a mafic parent and different crustal contaminants, produced the intermediate and siliceous hybrids in cupolas located above the main basaltic chamber. The types of country rock intruded as well as the degree of partial fusion achieved in individual cupolas controlled the range of hybrid compositions produced while the eruption sequence was determined by the order in which the cupolas were tapped. The second contamination event produced the plagioclase basalt, the most voluminous basaltic unit, by mixing the mafic parent with the olivine basalt, an independent, primary magma. Our results suggest crustal contamination models that assume bulk assimilation of crustal end members may be too simplistic.  相似文献   

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