Planetary and pre-solar noble gases in meteorites

Noble gases are not rare in the Universe, but they are rare in rocks. As a consequence, it has been possible to identify in detailed analyses a variety of components whose existence is barely visible in other elements: radiogenic and cosmogenic gases produced in situ, as well as a variety of “trapped” components – both of solar (solar wind) origin and the “planetary” noble gases. The latter are most abundant in the most primitive chondritic meteorites and are distinct in elemental and isotopic abundance patterns from planetary noble gases sensu strictu, e.g., those in the atmospheres of Earth and Mars, having in common only the strong relative depletion of light relative to heavy elements when compared to the solar abundance pattern. In themselves, the “planetary” noble gases in meteorites constitute again a complex mixture of components including such hosted by pre-solar stardust grains.The pre-solar components bear witness of the processes of nucleosynthesis in stars. In particular, krypton and xenon isotopes in pre-solar silicon carbide and graphite grains keep a record of physical conditions of the slow-neutron capture process (s-process) in asymptotic giant branch (AGB) stars. The more abundant Kr and Xe in the nanodiamonds, on the other hand, show a more enigmatic pattern, which, however, may be related to variants of the other two processes of heavy element nucleosynthesis, the rapid neutron capture process (r-process) and the p-process producing the proton-rich isotopes.“Q-type” noble gases of probably “local” origin dominate the inventory of the heavy noble gases (Ar, Kr, Xe). They are hosted by “phase Q”, a still ill-characterized carbonaceous phase that is concentrated in the acid-insoluble residue left after digestion of the main meteorite minerals in HF and HCl acids. While negligible in planetary-gas-rich primitive meteorites, the fraction carried by “solubles” becomes more important in chondrites of higher petrologic type. While apparently isotopically similar to Q gas, the elemental abundances are somewhat less fractionated relative to the solar pattern, and they deserve further study. Similar “planetary” gases occur in high abundance in the ureilite achondrites, while small amounts of Q-type noble gases may be present in some other achondrites. A “subsolar” component, possibly a mixture of Q and solar noble gases, is found in enstatite chondrites. While no definite mechanism has been identified for the introduction of the planetary noble gases into their meteoritic host phases, there are strong indications that ion implantation has played a major role.The planetary noble gases are concentrated in the meteorite matrix. Ca-Al-rich inclusions (CAIs) are largely planetary-gas-free, however, some trapped gases have been found in chondrules. Micrometeorites (MMs) and interplanetary dust particles (IDPs) often contain abundant solar wind He and Ne, but they are challenging objects for the analysis of the heavier noble gases that are characteristic for the planetary component. The few existing data for Xe point to a Q-like isotopic composition. Isotopically Q-Kr and Q-Xe show a mass dependent fractionation relative to solar wind, with small radiogenic/nuclear additions. They may be closer to “bulk solar” Kr and Xe than Kr and Xe in the solar wind, but for a firm conclusion it is necessary to gain a better understanding of mass fractionation during solar wind acceleration.     

Gamma-Ray Emission During the Accretion of Matter from a Supernova Envelope onto a Compact Remnant

The aim of this study is to investigate the accretion of matter onto a compact gravitating remnant (neutron star) in the central region of the expanding shell of a Type II supernova. Computations of an explosion with the energetics of a Type II supernova have been performed to derive the structure of matter in the vicinity of the neutron star. The energy of the expanding shell and the parameters of the presupernova correspond to the known values for SN 1987A. This accretion leads to the formation of a layer of fairly dense and hot gas at the surface of the compact remnant, providing the conditions for nucleosynthesis reactions. Thus, one result of the study is to demonstrate the importance of the r and rbc processes, or explosive nucleosynthesis, in the compact envelope of a neutron star. A second result is the production of emission lines from unstable elements formed in the central part of the neutron-star envelope.

     

Elemental Concentrations in Japanese Silicate Rock Standards JA-1, JR-1 and JB-2

Data on three Japanese geochemical reference samples (JR-1, JA-1, and JB-2) are presented. Ten major and thirty-five trace element concentrations were determined using x-ray fluorescence, instrumental thermal neutron activation, thermal neutron capture prompt gamma-ray spectrometry, delayed neutron assay, automated thermal neutron activation analysis, inductively coupled plasma emission, atomic absorption, and ion selective electrode. Good agreement between the various methods and with recent literature values were obtained using error weighted mean concentrations for the samples.     

Analyzing individual presolar grains with CHARISMA

Isotopic analysis of heavy elements in individual stardust grains is important in testing and constraining theories of stellar nucleosynthesis. These analyses are challenging in that the grains are very small, the largest being perhaps a few microns in diameter, and contain only trace concentrations of heavy elements, generally on the order of ppm. In addition, isotopic analysis requires the suppression of isobaric interferences. We describe a unique instrument, based on resonant ionization mass spectrometry, that has successfully characterized such grains for the past several years, and report on some recent upgrades that significantly enhance the instrumental capabilities. The fundamental principles and operational details are discussed, along with illustrative results and plans for future modifications.     

The use of neutrons and monochromatic X-rays for non-destructive testing in geological materials

In the paper we present our results for element sensitive high-energy X-ray tomography and high-speed thermal neutron tomography applied to geological samples. The tuneable monochromatic X-ray beam was used for element sensitive tomography of geological samples containing heavy elements using the K-edge dichromatic scanning technique. This type of NDT (non-destructive testing) allowed us to reveal the quantity and location of uranium, lead and mercury in Oklo samples (natural nuclear reactor) and Cinnabar stones. Fast 3-D thermal neutron imaging of dynamical processes was successfully tested at the high flux neutron tomography station of the ILL. The qualitative investigation of water repellents and consolidants applied on sandstones of Bray and limestones of Maastricht were the first samples to be studied with the new imaging technique.     

Chemical characterization of earth’s most ancient clastic metasediments from the Isua Greenstone Belt, southern West Greenland

New and published major and trace element abundances of clastic metasediments (mainly garnet-biotite-plagioclase schists) from the ∼3.8 Ga Isua Greenstone Belt (IGB), southern West Greenland, are used in an attempt to identify the compositional characteristics of the protoliths of these sediments. Compositionally, the metasediments are heterogeneous with enrichment of LREE (La/Sm_chond = 1.1-3.9) and variable enrichment and depletion of HREE (Gd/Yb_chond = 0.8-4.3). Chondrite-normalized Eu is also variable, spanning a range from relative Eu depletion to enrichment (Eu/Eu* = 0.6-1.3). A series of geochemical and geological criteria provides conclusive evidence for a sedimentary origin, in disagreement with some previous studies that questioned the presence of genuine clastic metasediments. In particular, trace element systematics of IGB metasediments show strong resemblance to other well-documented Archaean clastic sediments, and are consistent with a provenance consisting of ultramafic, mafic and felsic igneous rocks. Two schists, identified as metasomatized mafic igneous rocks from petrographic and field evidence, show distinct compositional differences to the metasediments.Major element systematics document incipient-to-moderate source weathering in the majority of metasediments, while signs of secondary K-addition are rare. Detailed inspection of Eu/Eu*, Fe₂O₃ and CIW (chemical index of weathering) relationships reveals that elevated iron contents (when compared to averages for continental crust) and strong relative enrichment in Eu may be due to precipitation of marine Fe-oxyhydroxides during deposition or diagenesis on the seafloor.Some of the IGB metasediments have yielded anomalous ¹⁴²Nd and ¹⁸²W isotopic compositions that were respectively interpreted in terms of early mantle differentiation processes and the presence of a meteorite component. Alternatively, W and possibly Nd isotopes could have been affected by thermal neutron capture on the Hadean surface. The latter process was tested in this study by analysis of Sm isotope compositions, which serve as an effective monitor for neutron capture effects. As no anomalous variation from terrestrial values was detected, we infer that isotope systematics (including ¹⁸²W and ¹⁴²Nd) of IGB metasediments were not affected by neutron capture, but reflect decay of radioactive parent isotopes.     

Determination of Boron in 35 International Geochemical Reference Materials by Thermal Neutron Capture Prompt Gamma-ray Spectrometry

Concentrations of boron in 35 silicate reference materials are measured by thermal neutron capture gamma-ray spectrometry. Results are compared for NBS, USGS, and CCRMP reference materials with values from the literature. The use of two prompt gamma facilities at Los Alamos are discussed.     

科学钻探中的元素测井技术

系统地介绍了科学钻探中应用自然伽玛能谱测井、活化测井、热中子俘获伽玛能谱测井和中子非弹性散射伽玛能谱测井确定元素含量的原理和方法;详细讨论了在不同的岩性条件下如何选择和建立从元素含量向矿物成分转换的模型。最后,介绍了元素测井技术在ＫＴＢ和ＯＤＰ中的应用,说明元素测井技术对重建岩性剖面、了解元素丰度和矿物成分的变化、研究矿物在高温高压下蚀变所涉及的地球化学作用、显示岩石的不均匀性和重建地球化学剖面等方面有特殊作用。此外,元素测井技术对于精确计算骨架密度、孔隙度和渗透率、井与井间相关对比,以及补足由于漏掉岩芯或岩屑而失去的有关信息,均具有重要作用。     

Geochemistry of eucrites: genesis of basaltic eucrites, and Hf and Ta as petrogenetic indicators for altered antarctic eucrites

We performed instrumental neutron activation analysis on a large suite of antarctic and nonantarctic eucrites, including unbrecciated, brecciated, and polymict eucrites and cumulate and noncumulate eucrites. We evaluate the use of Hf and Ta, two highly incompatible elements, as sensitive indicators of partial melting or fractional crystallization processes. Comparison with rare earth element (REE) data from nonantarctic and antarctic eucrites shows that Hf and Ta are unaffected by the terrestrial alteration that has modified the REE contents and patterns of some antarctic eucrites. The major host phases for Hf and Ta—zircon, baddeleyite, ilmenite, and titanite—are much less susceptible to terrestrial alteration than the phosphate hosts of REEs. The host phases for Hf and Ta are minor or trace phases, so sample heterogeneity is a serious concern for obtaining representative compositions. The trace lithophile and siderophile element contents of noncumulate eucrites do not allow for a single, simple model for the petrogenesis of the howardite-eucrite-diogenite suite. Fractional crystallization models cannot reproduce the compositional relationship between eucrites of the main group-Nuevo Laredo trend and those of the Stannern trend. Equilibrium crystallization models cannot explain the trace element diversity observed among diogenites. Partial melting models cannot explain the W variations among eucrites, unless source regions had different metal contents. We suggest that slight variations in oxygen fugacity of eucrite source regions during partial melting can explain the W variations without requiring different metal contents. This hypothesis may fail to account for eucrite Co contents, however.     

The chemical and physical characteristics of heavy metals in humus and till in the vicinity of the base metal smelter at Flin Flon, Manitoba, Canada

 Trace element geochemistry of humus (<0.425 mm) and till (<0.002 mm) collected in the Flin Flon-Snow Lake area, northern Manitoba and Saskatchewan, provides a regional context for assessing smelter contamination in the environment. The area includes a Cu-Zn smelter known to discharge As, Cd, Cu, Fe, Hg, Pb, and Zn. In this study, sequential extraction analyses, scanning electron microscopy and x-ray diffraction analyses were used on a suite of samples to determine: (1) the chemical and physical characteristics of heavy metals in surficial sediments related to distance from the smelter, (2) criteria for assessing the relative contribution of these metals from natural and anthropogenic sources, and (3) the potential of these metals for remobilization in the environment. Humus geochemistry reflects the anthropogenic and natural component of heavy metal concentrations. Smelter-related elements show anomalously high values adjacent to the smelter, decreasing with distance until background values are reached at 70–104 km, depending on the element. In humus, Zn is associated primarily with labile phases; Hg with non-labile phases. Adjacent to the smelter, high proportions and concentrations of Zn and Hg in non-labile phases, indicative of smelter-derived particulates, are confirmed by SEM examination. The particles occur as spheres, irregular grains, and with organics. With increasing distance from the smelter, the geochemical response to bedrock composition is more obvious than the anthropogenic input. Till geochemistry reflects the natural variation imposed by bedrock composition. At highly contaminated sites (<3 km from the smelter), increased percentages of smelter-related elements in labile phases suggests heavy metals are leached from humus to the underlying sediment. Received: 5 November 1996 · Accepted: 31 March 1997     

Determination of Rare Earth Elements in Geological Reference Materials: A Comparative Study by INAA and ICP-MS

Data was obtained for the rare earth elements (REE) by instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) in twenty geological reference materials. In general, the precision obtained by ICP-MS is better for the light REE, decreasing with increasing atomic number. This is partly a result of the occurrence of the heavy REE at low concentrations. The precision of the data obtained by INAA is good (5% RSD). The data obtained also showed that for the elements determined by both methods, the accuracy is similar for the light REE and better for the middle and heavy REEs by INAA. Higher uncertainty is achieved by ICP-MS mainly for elements at very low concentrations, occurring at about ten times the chondritic values.     

Mineralogical study of secondary mineral phases from weathered MSWI bottom ash: implications for the modelling and trapping of heavy metals

A mineralogical study of 3 samples of municipal solid waste incineration bottom ash collected from different storage sites and with storage times varying from 3 weeks to 2 years, has enabled identification of the main secondary mineral species formed during weathering. The frequencies of the secondary phases were determined and a diagram is proposed for the relative distribution of the newly formed mineral phases: calcite ≫ Fe oxides quartz ⩾ sulphates and/or ettringite (depending on the amount of reactive Al present in the bottom ash). This approach, involving careful sampling, sample preparation and the combined use of various analytical techniques, also showed the high frequency of Al hydroxides and amorphous phases and helped to identify more than 30 sulphates s.l. (sulphates, chromates, vanadates, etc.). Most of the secondary minerals (carbonates and sulphates s.l.) have broad metal trapping capacities for heavy element uptake (Pb, Zn, Cd, As, V, Cr, etc.) due to their crystal-chemistry characteristics. Ca-oxalates were also identified. Mineralogical data from the study provide new input for thermochemical models. The relative stability of metal uptake and the extent of associated neogenesis occurring during bottom-ash decomposition is discussed. Sulphate minerals (and certain heavy metal oxides (zincite)), which are extremely sensitive to environmental conditions, can trap metals only temporarily, as opposed to Fe oxyhydroxides (As, etc.) and carbonates (Pb, Zn, Cd), which are more stable under atmospheric conditions and constitute more sustainable trapping media with higher liquid/solid (L/S) ratios. Finally, a composite predictive diagram is proposed for the mineralogical evolution of bottom ash that accounts for variations in L/S ratios.     

Regolith history of the aubritic meteorite parent body revealed by neutron capture effects on Sm and Gd isotopes

Enstatite achondrites (aubrites) when compared to other stone meteorites have unusually long cosmic-ray exposure (CRE) ages. We report here the ¹⁵⁰Sm/¹⁴⁹Sm and ¹⁵⁸Gd/¹⁵⁷Gd ratios in six different structural phases, i.e., light and dark (shocked) grains and in matrix materials of Pesyanoe, in three different fragments from Pena Blanca Spring, and in one from Norton County, Shallowater, and Khor Temiki, to investigate the regolith history on the aubrite parent body. The results from phases components of Pesyanoe confirm earlier reported evidence for regolith irradiation of several aubrites. The inferred neutron fluences for six Pesyanoe separates vary between (2.13 and 2.82) × 10¹⁶ n cm⁻². The fluences also significantly exceed those expected from cosmic-ray irradiation during transit to Earth and approach those observed in the lunar regolith. These observations confirm that the brecciated Pesyanoe meteorite, which contains solar wind (SW) gases only in dark phases, was processed in a regolith and that structural phases were differentially irradiated before compaction. On the other hand, in some aubrites (Mt. Egerton, Shallowater, Pena Blanca Spring, Norton County) neutron capture effects may entirely be due to space irradiation.     

根系土中重金属元素分布特征及在农作物中的迁移

以上海市金山区为对象,分析了农用地土壤重金属元素的形态分布特征,以及元素的有效态（水溶态、离子交换态）与全量、有机质、pH等的相关性;根据重金属元素在稻米、蔬菜等不同农作物中的含量,分析了其迁移及生物有效性。结果表明：不同元素的形态组成差异较大;Pb、Zn、Ni元素的有效态与环境因素（pH、有机质）关系密切;土壤中重金属元素Cd最为活跃且易发生迁移,在多种农作物中有较为明显的富集;稻米中重金属元素的富集程度相对较小。研究成果可为土壤污染治理、种植结构调整、土地合理利用提供有益借鉴。     

Chemical characteristics of migmatites: accessory phase distribution and evidence for fast melt segregation rates

 Equilibration between melt and solid is inhibited by rapid melt extraction and by restricted equilibration (armouring, slow dissolution). When segregation occurs by channelised migration along high-porosity pathways, melt migration is more rapid than trace element diffusion rates in silicates and faster than accessory phase dissolution rates. Evidence for channelised flow and deformation-enhanced melt segregation into boudin necks, fractures and micro-shears at low melt fractions is present in the Moine Kirtomy Migmatitie Suite (KMS) in Sutherland, Scotland. Melt migration distances are on a metre to tens of metres scale. Concordant leucosomes in stromatic migmatities in the KMS have low Zr contents, low LREE (light rare-earth element) and H (heavy) REE contents and positive Eu anomalies. REE patterns of this type can be produced by removal of leucosome before complete equilibration with source due to the inhibited dissolution of LREE- and HREE-bearing accessory phases in water-undersaturated melts. Melting in the KMS, however, occurred at or near the wet granite solidus, leaving biotite as a residual phase. Detailed back-scattered electron imaging shows that REE-bearing accessory phases remained as residual phases, and were concentrated in the melanosome and at the melanosome-leucosome boundary. Irregularly shaped patches of diatexite contain a small proportion of excess Zr, consistent with entrainment of melanosome-schlieren enriched in zircon. These data indicate that deformation-enhanced melt extraction led to the rapid migration of small melt fractions from the melting site on a time-scale less than that required to saturate the melt in Zr. Leucosomes were thus prevented from equilibrating with accessory phases before extraction. Received: 12 July 1995 / Accepted: 4 March 1996     

I-Xe dating: intercomparisons of neutron irradiations and reproducibility of the Bjurböle standard

Parameters for a number of neutron irradiations are examined and results intercompared for the Bjurböle meteorite; data for the 1967 Valecitos-1 irradiation are presented. Apparent I-Xe ‘formation’ ages are reproducible for three different samples of Bjurböle, suggesting isotopic homogeneity for initial iodine in the bulk material. The systematics of neutron capture in ¹³⁵Xe (produced from ²³⁵U neutron fission) are examined and verified in irradiated BCR-1.     

A new look at anomalous X-ray Pulsars

We explore the possibility of explaining Anomalous X-ray Pulsars (AXPs) and Soft Gammaray Repeaters (SGRs) in a scenario with fall-back magnetic accretion onto a young isolated neutron star. The X-ray emission of the pulsar in this case originates due to the accretion of matter onto the surface of the neutron star from a magnetic slab surrounding its magnetosphere. The spin-down rate of the neutron star expected in this picture is close to the observed value. We show that such neutron stars are relatively young and are going through the transition from the propeller state to the accretor state. The pulsar’s activity in gamma-rays is connected with its relative youth, and is enabled by energy stored in a non-equilibrium layer located in the crust of the low-mass neutron star. This energy can be released due to the mixing of matter in the neutron star crust with super heavy nuclei approaching its surface and becoming unstable. The fission of nuclei in the low-density region initiates chain reactions leading to a nuclear explosion. Outbursts are probably triggered by instability developing in the region where the matter accreted by the neutron star accumulates in the magnetic polar regions.     

Trace element abundances and mineral/melt distribution coefficients in phonolites from the Laacher See volcano (Germany)

Twenty six whole rocks, seven matrix and fifty three mineral separates from the compositionally zoned late Quaternary Laacher See tephra sequence (East Eifel, W Germany) were analyzed by instrumental neutron activation. These data document the chemical variation within the Laacher See magma chamber prior to eruption with a highly fractionated phonolite at the top and a more mafic phonolite at its base as derived from other data. Incompatible elements such as Zn, Zr, Nb, Hf, U, light and heavy rare earths are extremely enriched towards the top whereas compatible elements (e.g. Sr, Sc, Co, Eu) are strongly depleted. Semicompatible elements (Ta and some middle REE) are depleted at intermediate levels. This chemical variation is shown by whole rock and matrix data indicating the phonolite liquid was compositionally zoned regardless of phenocryst content. Hybrid rocks (phonolite-basanite) show the largest concentrations for compatible elements. All elements (except Rb) display continuous compositional variations with regard to the stratigraphic position of pumice samples. From these data we are able to distinguish three main units: An early erupted highly fractionated magma, the main volume of evolved phonolite and a mafic phonolite as the final products. The extreme variation of trace element distribution coef ficients (K) for 9 mineral phases with respect to stratigraphic position (resp. matrix composition) cannot be explained by conventional mechanisms. We postulate a significant modification of the trace element content of the phonolite melt by liquid-liquid controlled differentiation processes subsequent to and/or contemporaneous with (fractional) crystallization which caused disequilibrium between phenocrysts and host matrix. Therefore, our “distribution coefficients” deviate from equilibrium partition coefficients equivalent to the amount of this post crystallization modification of the matrix composition. The relationship between varying K and matrix composition is demonstrated by a ΔK-ΔM-diagram (variation of K versus variation of matrix, M). Different parts of this diagram relate to different parameters (T, P, polymerization, complex-building, equilibrium crystallization in a zoned magma column and post crystallization disequilibrium effects) which are responsible for the variation of distribution coefficients in general. The ΔK-ΔM-diagram may allow to distinguish between different processes affecting the distribution coefficients measured in natural volcanic rocks from a differentiating magma system.     

Speciation of heavy metals in cement-stabilized waste forms: A micro-spectroscopic study

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of industrial and radioactive waste in underground repositories. In this study, synchrotron based-techniques (micro X-ray spectroscopy (XAS) and micro X-ray fluorescence (XRF)) were used to investigate Co and Ni uptake by Hardened Cement Paste (HCP) with the aim of improving our understanding of the immobilization process of heavy metals in cement at the molecular level. For Ni and Co, XRF mapping revealed a highly heterogeneous element distribution as far as the concentration is concerned. The XAS studies further showed that Ni(II) forms predominantly layered double hydroxide (LDH) phases. In contrast to Ni, Co was found to be present in the oxidation states II and III. Co(II) is predominately incorporated into newly formed Co(II) hydroxide-like phases (Co(OH)₂), Co-LDH or Co-phyllosilicates, whereas Co(III) tends to be incorporated into a Co(III)O(OH)-like phase or a Co-phyllomanganate.