NanoSIMS isotopic analysis of small presolar grains: Search for Si3N4 grains from AGB stars and Al and Ti isotopic compositions of rare presolar SiC grains

We report isotopic ratio measurements of small SiC and Si₃N₄ grains, with special emphasis on presolar SiC grains of type Z, and new nucleosynthesis models for ²⁶Al/²⁷Al and the Ti isotopic ratios in asymptotic giant branch (AGB) stars. With the NanoSIMS we analyzed 310 SiC grains from Murchison (carbonaceous CM2 chondrite) separate KJB (diameters 0.25-0.45 μm) and 153 SiC grains from KJG (diameters 1.8-3.7 μm), 154 SiC and 23 Si₃N₄ grains from Indarch (enstatite EH4 chondrite) separate IH6 (diameters 0.25-0.65 μm) for their C and N isotopic compositions, 549 SiC and 142 Si₃N₄ grains from IH6 for their C and Si isotopic compositions, 13 SiC grains from Murchison and 66 from Indarch for their Al-Mg compositions, and eight SiC grains from Murchison and 10 from Indarch for their Ti isotopic compositions. One of the original objectives of this effort was to compare isotopic analyses with the NanoSIMS with analyses previously obtained with the Cameca IMS 3f ion microprobe. Many of the Si₃N₄ grains from Indarch have isotopic anomalies but most of these apparently originate from adjacent SiC grains. Only one Si₃N₄ grain, with ¹³C and ¹⁴N excesses, has a likely AGB origin. The C, N, and Si isotopic data show that the percentage of SiC grains of type Y and Z increase with decreasing grain size (from ∼1% for grains >2 μm to ∼5-7% for grains of 0.5 μm), providing an opportunity for isotopic analyses in these rare grains. Our measurements expand the number of Al-Mg analyses on SiC Z grains from 4 to 23 and the number of Ti analyses on Z grains from 2 to 11. Inferred²⁶Al/²⁷Al ratios of Z grains are in the range found in mainstream and Y grains and do not exceed those predicted by models of AGB nucleosynthesis. Cool bottom processing (CBP) has been invoked to explain the low ¹²C/¹³C ratios of Z grains, but this process apparently does not lead to increased ²⁶Al production in the parent stars of these grains. This finding is in contrast to presolar oxide grains where CBP is needed to explain their high ²⁶Al/²⁷Al ratios. The low ^46,47,49Ti/⁴⁸Ti ratios found in Z grains and their correlation with low ²⁹Si/²⁸Si ratios extend the trend seen in mainstream grains and confirm an origin in low-metallicity AGB stars. The relatively large excesses in ³⁰Si and ⁵⁰Ti in Z grains are predicted by our models to be the result of increased production of these isotopes by neutron-capture nucleosynthesis in low-metallicity AGB stars. However, the predicted excesses in ⁵⁰Ti (and ⁴⁹Ti) are much larger than those found. Even lowering the strength of the ¹³C pocket cannot solve this discrepancy in a consistent way.     

Oxygen and hydrogen isotopic ratios in groundwaters and river waters from India

A comprehensive set of measurements of oxygen and hydrogen isotopic ratios in groundwaters as well as waters from rivers, lakes, hot springs etc. taken from a variety of locations in India has been carried out for the first time. Isotopically the most depleted samples occur in the high altitude precipitations in the Himalayas e.g. in the lakes of Bhutan and the source water of the Ganga. The shallow groundwater data display a continental effect where the heavy isotope content decreases with distance from the coast (about 4 to 6 per mil decrease in δ¹⁸O per 1000 km). The δ D and δ¹⁸O of these fresh waters are linearly related and an analysis of this relation vis-a-vis the meteoric water line shows the unambiguous effect of enrichment due to evaporation from soils.     

Oxygen isotopic ratios in fine quartz silt from sediments and soils of southern Africa

Fine quartz silt (1–10μm dia, important in aerosol dust) isolated from a large number of soils, as well as Phanerozoic shales, sandstones and recent sands of the southern African stratigraphie column (Carboniferous, Permian and Triassic) exhibits a mean δ¹⁸O of 12.2 ± 2.1%0. These values are similar to those reported for South Pacific pelagic sediments and adjacent land areas of similar latitude but are lower than those reported for this size fraction of 30 Mesozoic and Paleozoic shales (20.7 ± 1.8%.) and soils from mid-continental U.S.A., for aerosol quartz in the North Pacific pelagic sediments, and for eolian caps in high-elevation soils of Hawaii. The lower oxygen isotopic ratios in fine quartz silt of southern Africa reinforces the earlier indication that Southern Hemisphere detritai sedimentary reservoirs contain a higher proportion of igneous and metamorphic quartz (lower δ¹⁸O) and less lowtemperature authigenic quartz (higherδ¹⁸O) than Northern Hemisphere detritai sediments. The difference reflects climates, as continents drifted in latitude.     

Partition of magnesium and iron between Olivine and spinel,and between pyroxene and spinel

Partition of Fe²⁺ and Mg between coexisting (Mg, Fe)₂SiO₄ spinel and (Mg, Fe)SiO₃ pyroxene was investigated at pressures 80 and 90 kbar and at temperatures 840 and 1050° C, using tetrahedral-anvil type of high pressure apparatus. Olivine-spinel solid solution equilibria in the system Mg₂SiO₄-Fe₂SiO₄ were discussed in the light of the partition reaction. Partition of Fe²⁺ and Mg in both olivine-spinel and pyroxene-spinel systems can not be regarded as that between ideal solid solutions. By applying the simple solution model for the partition of Fe²⁺ and Mg, sign of the heat of mixing was estimated to be positive for all olivine, spinel and pyroxene. Relative concentration of Fe²⁺ in spinel in the pyroxene-spinel system is likely to cause some change in the chemical composition of modified spinel () or spinel () in the transition zone of the mantle. A considerable change is also expected in the transition pressure of to ( + ) and ( + ) to .Presented at the symposium Recent Advances in the Studies of Rocks and Minerals at High Pressures and Temperatures held in Montreal, 1972. Jointly sponsored by the International Mineralogical Association and the Commission on Experimental Petrology.     

Carbon and helium isotopic ratios at Kusatsu-Shirane Volcano,Japan

We have measured the chemical compositions, He/Ne ratios, He and C isotopes of 14 gas samples collected from the crater lake, fumaroles and hot springs associated with Kusatsu-Shirane Volcano, Japan. The³He/⁴He ratio decreases with increasing distance from the central crater of the volcano to the sampling site whereas the δ¹³C value of CO₂ increases with the distance. This tendency suggests that high³He/⁴He-low δ¹³C magmatic gas is mixed with and/or diluted by low³He/⁴He-high δ¹³C crustal gas with increasing distance from the crater. Alternatively, the variation of δ¹³C values may be the result of isotope fractionation during migration since the isotope shift is relatively small. Based on the apparent mixing trend in a³He/⁴He-δ¹³C diagram, the magmatic He and CO₂ in the volcano may have a³He/⁴He ratio of 8 R_atm and a δ¹³C value of −3.2%, respectively. The CO₂/³He ratios show a positive correlation with temperature of fumaroles or hot springs, which may be caused by a difference of temperature dependencies of the solubilities between CO₂ and He.     

Automated isotopic measurements of micron-sized dust: application to meteoritic presolar silicon carbide

We report the development of a new analytical system allowing the fully automated measurement of isotopic ratios in micrometer-sized particles by secondary ion mass spectrometry (SIMS) in a Cameca ims-6f ion microprobe. Scanning ion images and image processing algorithms are used to locate individual particles dispersed on sample substrates. The primary ion beam is electrostatically deflected to and focused onto each particle in turn, followed by a peak-jumping isotopic measurement. Automatic measurements of terrestrial standards indicate similar analytical uncertainties to traditional manual particle analyses (e.g., ∼3‰/amu for Si isotopic ratios). We also present an initial application of the measurement system to obtain Si and C isotopic ratios for ∼3300 presolar SiC grains from the Murchison CM2 carbonaceous chondrite. Three rare presolar Si₃N₄ grains were also identified and analyzed. Most of the analyzed grains were extracted from the host meteorite using a new chemical dissolution procedure. The isotopic data are broadly consistent with previous observations of presolar SiC in the same size range (∼0.5-4 μm). Members of the previously identified SiC AB, X, Y, and Z subgroups were identified, as was a highly unusual grain with an extreme ³⁰Si enrichment, a modest ²⁹Si enrichment, and isotopically light C. The stellar source responsible for this grain is likely to have been a supernova. Minor differences in isotopic distributions between the present work and prior data can be partially explained by terrestrial contamination and grain aggregation on sample mounts, though some of the differences are probably intrinsic to the samples. We use the large new SiC database to explore the relationships between three previously identified isotopic subgroups—mainstream, Y, and Z grains—all believed to originate in asymptotic giant branch stars. The isotopic data for Z grains suggest that their parent stars experienced strong CNO-cycle nucleosynthesis during the early asymptotic giant branch phase, consistent with either cool bottom processing in low-mass (M < 2.3M_⊙) parent stars or hot-bottom burning in intermediate-mass stars (M > 4M_⊙). The data provide evidence for a sharp threshold in metallicity, above which SiC grains form with much higher ¹²C/¹³C ratios than below. Above this threshold, the fraction of grains with relatively high ¹²C/¹³C decreases exponentially with increasing ²⁹Si/²⁸Si ratio. This result indicates a sharp increase in the maximum mass of SiC parent stars with decreasing metallicity, in contrast to expectations from Galactic chemical evolution theory.     

A NanoSIMS study of Si- and Ca-Ti-isotopic compositions of presolar silicon carbide grains from supernovae

We report results from NanoSIMS isotopic measurements on 37 presolar silicon carbide grains of type X which are believed to have formed in the ejecta of supernova explosions. Isotopic data were obtained for Si and Ca-Ti (all grains), C and N (two grains), and Ti (one grain). All X grains exhibit large enrichments in ²⁸Si (up to 5× solar), in agreement with previously studied X grains. On a scale of 200 nm, the Si-isotopic ratios do not vary by more than the analytical uncertainties of several percent in all but one X grain. This implies that most X grains formed from well-mixed regions in supernova ejecta. X grain M9-68-3 is characterized by two regions with distinct Si- and Ti-isotopic signatures which may either represent two distinct grains or overgrowth of matter from two different mixtures in the supernova ejecta. Most of the Ca in the X grains is most likely contamination as indicated by close to normal ⁴²Ca/⁴⁰Ca ratios. Seven X grains show enhanced ⁴⁴Ca/⁴⁰Ca ratios of up to 6× the solar ratio. Spatial distributions of ⁴⁴Ca excesses and Ti are positively correlated, giving strong support to the view that excesses in ⁴⁴Ca are due to the decay of radioactive ⁴⁴Ti. Inferred initial ⁴⁴Ti/⁴⁸Ti ratios are between 0.01 and 0.28 and are correlated with Si-isotopic ratios. Radiogenic ⁴⁴Ca is widely distributed in six X grains. X grain M9-132-4 exhibits a pronounced heterogeneity in the distribution of radiogenic ⁴⁴Ca and ⁴⁸Ti as well as in ⁴⁴Ti/⁴⁸Ti, pointing to presence of a small Ti-rich subgrain or heterogeneous loss of Ca and Ti after grain formation. This grain has a unique Si-isotopic composition with ³⁰Si/²⁹Si = 2.2× the solar ratio and C- and N-isotopic compositions as typically observed in X grains.     

Presolar Grains and Their Isotopic Anomalies in Meteorites

Study on presolar grains including diamond,silicon carbide,graphite,silicon nitrite(Si3N4),coundum and spinel isolated from meteorites is summarized in this paper.Except for nanometer-sized diamond,the other grains are micrometers to submicrometers in size.The presolar grains survived mainly in the fine-grained matrix of primitive chondrites and were isolated by chemical treatments.Diamond contains Xe isotopes(Xe-HL),typically produced in p-and r-processes,probably formed in supernovae.Mainstream silicon carbides are enriched in ^29,30Si and ^13C,but depleted in ^15N.They also contain various s-process products,consistent with calculations of AGB stars.Other silicon carbides exhibit much larger isotopic anomalies and are classified as groups X,Y,Z and AB.Among them,group X of SiC is characterized by enrichment of ^28Si and daughter isotopes of various short-lived nuclides,suggesting an origin from supernovae.Graphite can be divided into four density fractions with distince isotopic compositions.They may form in AGB stars,novae and supernovae,respctively,Si3N4 is similar to X-SiC in isotopic composition.Corundum is classified as four groups based on theid oxygen isotopic compositions.AGB and red giang stare are possible sources for the oxide.More comprehensive study of presolar grains,especially discovery of the other types of oxides and silicates,isotopic analyses of individual submicrometer-sized grains and distribution of presolar grains among various chemical groups and petropaphic types of chondrites will provide new information on nucleosynthesis,stellar evolution and formation of the solar nebula.     

Presolar spinel grains from the Murray and Murchison carbonaceous chondrites

With a new type of ion microprobe, the NanoSIMS, we determined the oxygen isotopic compositions of small (<1μm) oxide grains in chemical separates from two CM2 carbonaceous meteorites, Murray and Murchison. Among 628 grains from Murray separate CF (mean diameter 0.15 μm) we discovered 15 presolar spinel and 3 presolar corundum grains, among 753 grains from Murray separate CG (mean diameter 0.45 μm) 9 presolar spinel grains, and among 473 grains from Murchison separate KIE (mean diameter 0.5 μm) 2 presolar spinel and 4 presolar corundum grains. The abundance of presolar spinel is highest (2.4%) in the smallest size fraction. The total abundance in the whole meteorite is at least 1 ppm, which makes spinel the third-most abundant presolar grain species after nanodiamonds (if indeed a significant fraction of them are presolar) and silicon carbide. The O-isotopic distribution of the spinel grains is very similar to that of presolar corundum, the only statistically significant difference being that there is a larger fraction of corundum grains with large ¹⁷O excesses (¹⁷O/¹⁶O > 1.5 × 10⁻³), which indicates parent stars with masses between 1.8 and 4.5 M_⊙.     

茶叶中铅同位素比值的测定方法

为了给铅同位素示踪技术在研究茶叶中重金属铅来源的应用奠定基础,通过大量的茶叶炭化、灰化条件试验和铅的分离、纯化、富集与质谱测定试验,拟定了一套茶叶中铅同位素比值的测定方法:将称好的茶叶置于瓷坩埚中,在电热板上小火炭化完全后,移入马弗炉中灰化,用盐酸溶解灰分,转化为混合酸介质,然后上柱分离解吸,蒸干并上质谱测定.该法打破传统,改用盐酸溶解灰分,克服了用硝酸溶样总是有棕色沉淀物的难点.利用这一流程测得的茶叶样品的 207Pb/206Pb的精度( 2σ)优于± 0.05%. 208Pb强度一般均在 1 V以上.监控分析流程的国际标准物质 NBS 981的 207Pb/206Pb为 0.914 49± 0.000 04(其证书值为 0.914 64± 0.000 33),全流程本底铅为 1.6× 10-8量级.     

Oxygen,boron, chromium and niobium enrichment in native Au and Ag grains: A case study from the Linglong gold deposit,Jiaodong, eastern China

Quartz vein-type gold mineralization in the Linglong deposit constitutes one of the important sources of gold in China. Here we report the first finding of anomalous enrichment of boron (B), oxygen (O), chromium (Cr) and niobium (Nb) in native gold and Ag–Te grains from the Linglong deposit. The oxygen content of gold and silver grains ranges up to 75.83 at.%, boron up to 97.85 at.%, chromium up to 26.23 at.%, and tellurium up to 33.4 at.%. The Au precipitation is mainly linked to pyrite precipitation under reducing conditions. The HFSE enrichment including chromium (Cr) and niobium (Nb) in the gold and silver grains indicate that the ore-forming fluids were derived from high temperature magmas sourced from depth. The enrichment of low temperature Te in the native gold and silver grains, combined with the typical features of fluid ‘boiling’ as inferred from fluid inclusion studies indicate that the ore-fluids derived from depth upwelled rapidly, and metal precipitation occurred through decompression at shallower levels. Our results suggest good prospect for gold and silver at depth in Linglong.     

The distribution of chromium among orthopyroxene,spinel and silicate liquid at atmospheric pressure

A series of experiments has been carried out in which a synthetic silicate melt, of composition equivalent to a “U-type” Bushveld Complex parent liquid, was equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151°C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wüstite buffers. The partition coefficient for Cr between bronzite and melt increases with falling temperature along a given oxygen buffer, and decreases with falling oxygen fugacity at a given temperature, showing an overall range from 1.1 to 11.7. The Cr content of the melt in equilibrium with spinel (Cr solubility) decreases with falling temperature and increases with lower oxygen fugacity. This variation may be quantified in terms of temperature-dependent solubility of Cr³⁺ combined with a changing ratio of Cr³⁺ to Cr²⁺ in the melt. Iso-oxidation curves for Cr are approximately parallel to Fe-Si-O buffer curves and to curves for equal Fe³⁺/Fe²⁺ determined by Hill and Roeder (1974), and agree within experimental error with the results of Schreiber and Haskin (1976). When the changing oxidation state of Cr is allowed for, the orthopyroxene partition coefficient may be expressed as the sum of the temperature-dependent coefficient for Cr³⁺ and a partition coefficient of about 1 for Cr²⁺.The experimental results are used to construct a series of model curves for liquid and bronzite compositional variations during fractional crystallization of a Bushveld parent liquid. Trends for Cr variation are shown to depend critically upon oxygen fugacity, and on whether the liquid is saturated with chromite. The position of the peritectic between chromite and orthopyroxene is shown to be very sensitive to oxygen fugacity within one and a half log units of the QFM buffer. This observation may explain the contrasting distribution of chromite seams in the Bushveld Complex, where chromite occurs within bronzitite-norite sequences, and in the Stillwater Complex in which chromite is restricted to olivine cumulate layers.     

Auger Nanoprobe analysis of presolar ferromagnesian silicate grains from primitive CR chondrites QUE 99177 and MET 00426

We have investigated the presolar grain inventories of two CR chondrites, QUE 99177 and MET 00426, which are less altered than most members of this meteorite group. Both meteorites contain high abundances of O-anomalous presolar grains, with concentrations of 220 ± 40 and 160 ± 30 ppm for QUE 99177 and MET 00426, respectively. The presolar grain inventories are dominated by ferromagnesian silicates with group 1 oxygen isotopic compositions, indicative of origins in low mass red giant or asymptotic giant branch stars. Grains with pyroxene-like compositions are somewhat more common than those with olivine-like compositions, but most grains are non-stoichiometric with compositions intermediate between these two phases, consistent with recent work suggesting that amorphous interstellar silicates have stoichiometries between olivine and pyroxene type silicates. Although structural data are not available, one grain contains only Si and O, and has a stoichiometry consistent with SiO₂.Our presolar grains are much more Fe-rich than predicted by astronomical observations. Although secondary alteration may play a role in enhancing the Fe contents of presolar grains, it seems unlikely that the large and ubiquitous Fe enrichments observed in the grains from this study can be due only to secondary processing, particularly given the highly primitive nature of these two meteorites. Grain condensation in the stellar outflows where these grains formed likely proceeded under rapidly changing kinetic conditions that may have enhanced the incorporation of Fe into the grains over that expected based on equilibrium condensation theory.Both QUE 99177 and MET 00426 appear to contain unusually low abundances of oxide grains and have higher silicate/oxide ratios than other primitive meteorites analyzed to date. We explore various possibilities for this discrepancy, but note that most scenarios are not likely to result in the preferential destruction of oxides relative to silicates. Thus, the highest silicate/oxide ratios, such as those observed in the CR chondrites, should reflect the true initial proportions of presolar silicate and oxide grains in the parent molecular cloud from which the solar nebula evolved.     

Strontium and lead isotopic ratios,heterogeneous accretion of the Earth,and mantle plumes

If the Earth formed by accretion of volatile-rich material on to a refractory, primitive body with incomplete subsequent mixing, old or deep-seated igneous rocks should exhibit an anti-correlation between radiogenic Pb and radiogenic Sr. The ancient Amîtsoq gneiss and some modern oceanic rocks appear to comply with this model. Mantle plumes should not be a source of radiogenic Sr.     

Lithium isotopic disequilibrium of minerals in the spinel lherzolite xenoliths from Boeun,Korea

Spinel lherzolite xenoliths found in Boeun, Korea, have protogranular to porphyroclastic textures and are enclosed in a Miocene alkali basalt. The lithium concentration and isotopic compositions of olivine, clinopyroxene, and orthopyroxene separates from the spinel lherzolite, and whole rocks of the spinel lherzolites and alkali basalt were determined by inductively coupled plasma mass spectrometry (ICP-MS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The lithium concentrations of the olivines and orthopyroxenes range from 2.2 to 5.0 ppm and from 2.1 to 6.4 ppm, respectively. In contrast, the clinopyroxenes have larger lithium concentrations, from 2.0 to 8.4 ppm, which reflect their preferential lithium enrichment. The lithium isotopic compositions (δ⁷Li) of olivines (-5.4 to + 3.5‰), orthopyroxenes (-11.4 to -0.1‰), and clinopyroxenes (-14.4 to -4.7‰) range far beyond the average mantle composition of + 4 ± 2‰. The lithium isotopic composition of the host rock, alkali basalt (3.4‰), is within the range of the intraplate and oceanic island basalts. The spinel lherzolites from Boeun exhibits strong elemental and isotopic disequilibria due to the different lithium and lithium isotope diffusion velocities in the olivine, orthopyroxene, and clinopyroxene minerals after eruption and magma cooling.     

Precise determination of SmNd ratios,Sm and Nd isotopic abundances in standard solutions

The methods used for precise calibrations of $\text{Sm}\text{Nd}$ ratios and the average isotopic abundances obtained for normal Sm and Nd are given. A mixed Sm-Nd normal solution with a precisely known ${}^{147}\text{Sm}{}^{144}\text{Nd}$ ratio close to the nominal average chondritic value is described and the calibration discussed. Aliquots of this standard solution are available on request and may be useful for precise interlaboratory calibration of Sm and Nd.     

Oxygen isotopic composition and U-Pb discordance in zircon

We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution δ¹⁸O measurement by ion microprobe. δ¹⁸O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) δ¹⁸O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in ¹⁸O, but the relationship between discordance and δ¹⁸O is not systematic. δ¹⁸O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and δ¹⁸O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of ¹⁸O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in ¹⁸O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in δ¹⁸O, leave their imprint on both the texture and U-Pb systematics of zircon.     

海洋沉积物的铁和锌同位素测定

介绍海洋沉积物Fe和Zn同位素化学前处理及测定方法,报道南海西部夏季上升流区两个沉积物柱样的Fe和Zn同位素组成。样品采用HF+HNO3+HClO4常压消解,经脱盐后,转化为氯化物形式并经离子交换柱分离纯化后,用多接收器等离子体质谱法测定Fe和Zn同位素比值。该前处理方法可以快捷地实现海洋沉积物的消解、有机质的去除和海盐脱离;结合相关测试流程,可获得较高的δ56Fe(0.10‰,2SD)和δ66Zn分析精度(0.11‰,2SD)。两个沉积物柱样的δ56Fe值(相对于IRMM-014)和δ66Zn值(相对于JMC3-0749C)随深度变化不明显,两柱之间也无明显差异。总体上,南海西部上升流区1～2 ka以来的沉积物δ56Fe值(0.04‰～0.20‰)和δ66Zn值(0.12‰～0.30‰)与已报道的黄土和气溶胶、火成岩以及大部分海洋沉积物接近,明显高于静海相海洋沉积物的δ56Fe值。