Ca-rich Inclusions Research Articles

Some critical observations about the degradation of glass: The formation of lamellae explained

This study demonstrates that the mechanism responsible for the transformation of glass into a degradation layer is pH-dependent. In acid conditions, the transformed glass is homogeneous and brittle. In mild alkaline conditions, transformed glass is heterogeneous due to the presence of lamellae composed of silica nanoparticles and the occurrence of Ca-rich inclusions. The fundamental difference between acid and alkaline conditions cannot be explained by the currently accepted degradation mechanism based on ion exchange. To explain this critical observation, we propose a refined degradation mechanism based on existing knowledge that involves several inwardly moving reaction fronts. The fronts responsible for the transformation of the silicate network into amorphous silica are also responsible for the morphology of the transformed glass. We have identified the feedback mechanism that explains the formation of lamellae in alkaline conditions.

The mineralogy of Ca-rich inclusions in sublithospheric diamonds

This paper discusses mineralogy of Ca-rich inclusions in ultra-deep (sublithospheric) diamonds. It was shown that most of the Ca-rich majoritic garnets are of metabasic (eclogitic) affinity. The observed variation in major and trace element composition is consistent with variations in the composition of the protolith and the degree of enrichment or depletion during interaction with melts. Major and trace element compositions of the inclusions of Ca minerals in ultra-deep diamonds indicate that they crystallized from Ca-carbonatite melts that were derived from partial melting of eclogite bodies in deeply subducted oceanic crust in the transition zone or even the lower mantle. The occurrence of merwinite or CAS inclusions in ultra-deep diamonds can serve as mineralogical indicators of the interaction of metaperidotitic and metabasic mantle lithologies with alkaline carbonatite melts. The discovery of the inclusions of carbonates in association with ultra-deep Ca minerals can not only provide additional support for their role in the diamond formation process but also help to define additional mantle reservoirs involved in global carbon cycle.

Effects of the composition of Ca-rich inclusions on tool wear mechanisms during the hard-turning of steels for transmission components

This study describes the influence of the steel characteristics of Ca-treated carburising steel grades during hard part turning of synchronising rings in gearbox production. The main focus was on the chemical composition of the non-metallic inclusions in the evaluated workpieces and their effect on the PCBN tool wear. In addition, a Ca-treated carburising steel grade was compared to a standard steel grade.Machining tests were performed at the transmission machining site at Scania in order to evaluate the PCBN cutting tool life as defined by the generated surface roughness during actual production. The progression of flank and crater wear was evaluated by using a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDS) and a secondary electron (SE) detector.The Ca-treated steel showed a more than doubled tool life than that of the standard steel grade. The superior machinability was linked to the formation of a Ca-enriched slag barrier composed of (Mn,Ca)S and (Ca,Al)(O,S). It is believed that the stability of the protective deposits is essential to minimise diffusion-induced chemical wear of the PCBN tool.

The CO chondrites: Major recent Antarctic finds, their thermal and radiation history, and describing the metamorphic history of members of the class

Thermoluminescence (TL) properties of 29 CO chondrites from the Miller Range (MIL) and five chondrites from the Dominion Range (DOM) have been measured. MIL has a relatively strong natural TL signal (19.6±14.7krad), while some of the DOM samples have a very weak natural TL signal (<1krad) whereas others resemble the MIL meteorites. I argue that MIL and some of the DOM samples had a normal perihelion (∼1.0AU) and terrestrial age of ∼450–700ka, while some of the DOM samples have a terrestrial age of ∼100ka but a perihelion of ∼0.8AU. The DOM meteorites also show considerable heterogeneity in their induced TL properties, also suggesting that the DOM fragments represent more than one fall. The induced TL data for the MIL samples studied here are consistent with them all being from a single fragmented meteorite. Small (50mg) chips have TL properties similar to 500mg chips, so that the smaller chips are representative, although samples taken from original masses less than ∼2g have low natural TL suggesting that they were heated during atmospheric fall. The properties of CO chondrites are reviewed in terms of their petrologic types. Correlations between TL sensitivity, the most quantitative technique for evaluating metamorphic alteration in CO chondrites, and data for olivine composition and heterogeneity, matrix composition, inert gas content, metal composition (Ni, Co, and Cr in the kamacite), bulk carbon, C and O isotopes, graphite ordering, spectral reflectance at 0.8μm, and textural characteristics of the ameboid olivine and Ca-rich inclusions are examined. The petrographic types appear to be largely metamorphic in origin with perhaps a minor role for metasomatism. Contrary to recent proposals it is here argued that petrologic type definitions should (1) be specific enough to be meaningful, but broad enough to be simple in application and robust to new developments, (2) be descriptive and not interpretative, (3) should not oversimplify and obscure important class-to-class differences, and (4) take account of all the available information, while avoiding reliance on any one technique or single observation whose application is based on interpretation. With these considerations in mind the petrographic type definitions for CO chondrites are restated and the petrologic type of 3.2 assigned to both the MIL and DOM CO chondrites.

Three-Dimensional Fe Speciation of an Inclusion Cloud within an Ultradeep Diamond by Confocal μ-X-ray Absorption Near Edge Structure: Evidence for Late Stage Overprint

A stream of 1-20 μm sized mineral inclusions having the negative crystal shape of its host within an "ultra-deep" diamond from Rio Soriso (Juina area, Mato Grosso State, Brazil) has been studied with confocal μ-X-ray absorption near edge structure (μXANES) at the Fe K and Mn K edges. This technique allows the three-dimensional nondestructive speciation of the Fe and Mn containing minerals within the inclusion cloud. The observed Fe-rich inclusions were identified to be ferropericlase (Fe,Mg)O, hematite and a mixture of these two minerals. Confocal μ-X-ray fluorescence (μXRF) further showed that Ca-rich inclusions were present as well, which are spatially separated from or in close contact with the Fe-rich inclusions. The inclusions are aligned along a plane, which most likely represents a primary growth zone. In the close vicinity of the inclusions, carbon coated planar features are visible. The three-dimensional distribution indicates a likely fluid overprint along an open crack. Our results imply that an imposed negative diamond shape of an inclusion alone does not exclude epigenetic formation or intense late stage overprint.

Silicate and carbonate melt inclusions associated with diamonds in deeply subducted carbonate rocks

Abstract Deeply subducted carbonate rocks from the Kokchetav massif (Northern Kazakhstan) recrystallised within the diamond stability field ( P = 4.5–6.0 GPa; T ≈ 1000 °C) and preserve evidence for ultra high-pressure carbonate and silicate melts. The carbonate rocks consist of garnet and K-bearing clinopyroxene embedded in a dolomite or magnesian calcite matrix. Polycrystalline magnesian calcite and polyphase carbonate–silicate inclusions occurring in garnet and clinopyroxene show textural features of former melt inclusions. The trace element composition of such carbonate inclusions is enriched in Ba and light rare earth elements and depleted in heavy rare earth elements with respect to the matrix carbonates providing further evidence that the inclusions represent trapped carbonate melt. Polyphase inclusions in garnet and clinopyroxene within a magnesian calcite marble, consisting mainly of a tight intergrowth of biotite + K-feldspar and biotite + zoisite + titanite, are interpreted to represent two different types of K-rich silicate melts. Both melt types show high contents of large ion lithophile elements but contrasting contents of rare earth elements. The Ca-rich inclusions display high REE contents similar to the carbonate inclusions and show a general trace element characteristic compatible with a hydrous granitic origin. Low SiO 2 content in the silicate melts indicates that they represent residual melts after extensive interaction with carbonates. These observations suggest that hydrous granitic melts derived from the adjacent metapelites reacted with dolomite at ultra high-pressure conditions to form garnet, clinopyroxene – a hydrous carbonate melt – and residual silicate melts. Silicate and carbonate melt inclusions contain diamond, providing evidence that such an interaction promotes diamond growth. The finding of carbonate melts in deeply subducted crust might have important consequences for recycling of trace elements and especially C from the slab to the mantle wedge.

A modified crush-leach method for the analysis of fluid inclusion electrolytes

A procedure is described which has yielded chemical analyses for 15 elements from inclusion fluids trapped in quartz, and requires about 10 g of cleaned sample. Problems of contamination and adsorption that have bedeviled crush-leach analysis in the past have been overcome and good charge balances obtained. New data are presented on the adsorption of ions released during crush-leach analysis onto the new quartz surfaces generated. These show very significant losses of divalent cations from solution when using pure water as a leachate, thus leading to systematic analytical errors. Further experiments were conducted using H+ and La3+ in the leach solution as adsorption inhibitors and from the results a new crush-leach analysis procedure is proposed in which errors due to adsorption effects are minimal. The new technique utilises a variety of leaches tailored to minimise adsorption of specific ions, while being compatible with standard analytical procedures. Methods of analysis used are Atomic Absorption Spectrometry, Flame Emission Spectrometry, ICP-AES, Mass Spectrometry, Fluorimetry and Specific Ion Electrode. At present analyses can be performed for Na, K, Li, Rb, Ca, Mg, Sr. Ba, Fe, Mn, Zn, Al, Cl, B and F. Preliminary results on inclusions in quartz veins from both low and high grade metamorphic rocks show good agreement with theoretically predicted compositions from fluid-mineral equilibria for Na, K, Fe, Mn and Zn. However Ca and sometimes Mg are present at levels far higher than predicted. This is thought to be due to the presence of Ca-rich inclusions (which have been identified microthermometrically in some of the samples). A second set of data from post-metamorphic gold bearing quartz veins from the Monte Rosa district of Italy, where only one generation of inclusion fluids is present, show better agreement with calculated compositions with no excess Ca or Mg.

Trace elements in the Allende meteorite—II. Fine-grained. Ca-rich inclusions

Nine fine-grained feldspathoid-, grossular-, spinel-, pyroxene-bearing inclusions from the Allende meteorite were analysed by instrumental neutron activation analysis. On the average, these inclusions are enriched in the refractory lithophile elements Ca, Sc, Ta and the rare earths by factors of 5–30 relative to Cl chondrites but are depleted in the refractory and volatile siderophiles, Ir, Co and Au. The volatile elements Fe, Cr and Zn are present at levels of 3.38–8.51%, 326–2516 ppm and 308–1376 ppm, respectively. Textural, mineralogical and chemical data suggest that the fine-grained inclusions formed in the solar nebula by the simultaneous condensation of volatiles and refractory lithophile elements which failed to condense into the coarse-grained, high-temperature condensate inclusions. The marked differences in the enrichment factors for different refractories in the fine-grained inclusions are caused by relatively small differences in their accretion efficiencies into the coarse-grained ones. The trace element data indicate that the refractories in the fine- and coarse-grained inclusions can only be the cosmic complements of one another if the fine-grained ones represent no more than ~ 20% of the most abundant refractory elements.

The case for an unfractionated 244Pu/ 238U ratio in high-temperature condensates

The coarse-grained, Ca-rich inclusions in the Allende meteorite are the highest-temperature condensates from the cooling solar nebula and, as such, the oldest solid objects in the solar system. All refractory elements with condensation points above the accretion temperature of the inclusions whose concentrations in them have been measured are seen to be present in the inclusions in unfractionated proportion to one another relative to C1 chondrites when data are averaged for a large number of inclusions. Observational data for U and theoretical data for both U and Pu suggest that these elements exhibited refractory behavior in the solar nebula. An experiment is proposed in which fissiogenic Xe and U contents are measured in a suite of these inclusions to obtain the 244Pu/ 238U ratio of the solar system at the time of initial condensation with an uncertainty of ±15%.

X-ray topographic study of defects in olivine crystals

The dislocation structure in olivine crystals has been studied by means of X-ray topography. The dislocations have Burgers vector [100] or [001], the majority of the dislocations lying in the (100) or the (001) plane and being of the edge, screw or mixed type. Some dislocation tangles are apparently closely connected to Ca-rich inclusions. The observed dislocation structure and its possible origins are discussed in relation to previous electron diffraction studies and slip line observations on olivine crystals deformed naturally or experimentally at various temperatures.

Petrography and mineral chemistry of Ca-rich inclusions in the Allende meteorite

There are two types of white, coarse-grained, Ca-Al-rich inclusions in Allende. Type A inclusions contain 80–85 per cent melilite, 15–20 per cent spinel, 1–2 per cent perovskite and rare plagioclase, hibonite, wollastonite and grossularite. Clinopyroxene, if present, is restricted to thin rims around inclusions or cavities in their interiors. Type B inclusions contain 35–60 per cent pyroxene, 15–30 per cent spinel, 5–25 per cent plagioclase and 5–20 per cent melilite. The coarse pyroxene crystals in Type B's contain >15 per cent Al 2O 3 and >1.8 per cent Ti, some of which is trivalent. Type A pyroxenes contain <9 per cent Al 2O 3 and <0.7 per cent Ti. Electron microprobe analyses of 600 melilite, 39 pyroxene, 35 plagioelase, 33 spinel and 20 perovskite grains were performed in 16 Type A, 1 intermediate and 9 Type B inclusions in Allende and 1 Type A in Grosnaja. Melilite composition histograms from individual Type A inclusions are usually peaked between Ak10 and Ak30 and are 15–20 mole % wide while those from Type B inclusions are broader, unpeaked and displaced to higher åkermanite contents. Most pyroxenes contain < 1 per cent FeO. All plagioclase is An 98 to An 100. Spinel is almost pure MgAl 2O 4. Perovskite contains small (< 1 per cent) but significant amounts of Mg, Al, Fe, Y, Zr and Nb. Inferred bulk chemical compositions of Type A inclusions are rather close to those expected for high-temperature condensates. Those of Type B inclusions suggest slightly lower temperatures but their Ca/Al ratio seems less than the Type A's, indicating that the Type B's may not be their direct descendants. Some textural features suggest that the inclusions are primordial solid condensetes while others indicate that they may have been melted after condensation. Fragmentation and metamorphism may have also occurred after condensation.