Monte Carlo simulations of the dissolution of borosilicate and aluminoborosilicate glasses in dilute aqueous solutions

The aim of this study was to use Monte Carlo simulations to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses in dilute aqueous solutions. In the first part of this work, the effects of different structural features, such as the presence of non-bridging oxygens (NBO) or the formation of boroxol rings, on glass dissolution were evaluated separately and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of NBO was found to be linear at all Si/B ratios and the accelerating effect of NBO was shown to increase with increasing Si/B ratio. (2) The formation of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution.In the second part of this work, the dissolution of the NeB glasses studied by Pierce et al. (2010) was modeled in dilute aqueous solutions. Pierce et al. concluded from their study that either the rupture of the Al-O bonds or that of the Si-O bonds was the rate-limiting step controlling the dissolution of the NeB glasses. The simulations refined this conclusion and showed that, at low B/Al ratios, the rupture of both Al-O-Si and Si-O-Si linkages contributed to the dissolution rate whereas, at high B/Al ratios, the dissolution rate was independent of the rupture of Al-O-Si linkages and was controlled by S¹ sites (silicon sites at the glass-water interface with one connection to nearest-neighbor sites) and dissolution via detachment of clusters.     

Analysis of petrologic hypotheses with Pearce element ratios

Pearce element ratios can test whether the members of a rock suite are comagmatic and can illustrate the causes of chemical diversity in comagmatic suites. Comagmatic rocks have constant ratios for elements conserved in the system during changes that led to the chemical diversity. In basaltic systems, the incompatible elements, Ti, K, and P, are often conserved. The slope of the trend on a Pearce element ratio diagram is sensitive to the stoichiometry of the crystallizing and segregating phases. A judicious choice of ratios as axes for the diagram provides a signature for the phases involved and estimates of their compositions. In basaltic rocks, diagrams with Ti/K vs P/K can provide a test of the comagmatic hypothesis. Diagrams with 0.5 [Mg + Fe]/K vs Si/K have trends that are distinct for each comagmatic suite and different mineral assemblage. Different suites are distinguished by the intercepts in diagrams, whereas mineral assemblages are recognized by the slopes of the trends. For example, if olivine is the sole crystallizing and segregating phase, the trend will have a slope of 1. Diagrams with [2Ca + Na]/K vs Al/K distinguish plagioclase from augite assemblages and, in conjunction with 0.5 [Mg + Fe]/K diagrams, unravel the crystallization sequences of suites that have suffered three phase crystallization and segregation. Analyses from the Uwekahuna laccolith, Kilauea, the 1955 and 1967–68 eruptions of Kilauea, Diamond Craters Volcanic Field, Oregon, and experimental data on MORB glasses provide illustrations of the interpretations that can be obtained from Pearce element ratios.     

Vibrational interactions of tetrahedra in silicate glasses and crystals

Normal coordinate calculations, producing synthetic infrared and Raman spectra, were carried out on melilites, pyroxenes, silica polymorphs and feldspars. Atomic motions are complex in the high-frequency Raman modes of melilites and aluminous pyroxenes. The symmetric T-Onb stretching vibrations of Si and Al tetrahedra with different numbers of bridging oxygens are separate from each other, but may combine individually with oscillation of bridging oxygens between Si and Al tetrahedra. The latter type of vibration tends to dominate as Al/Si increases. The frequencies of these vibrational components and the degree of such intermixing depend on T-O force constants, which vary greatly depending on local bonding configurations; individual bands in the high-frequency Raman cannot in general be assigned to single structural entities or fixed combinations thereof. Calculations confirm that in some Al-Si glasses such as jadeite and spodumene, i.e. those in which all Al can be tetrahedral without non-bridging oxygens, Al-O-Al linkages or linkage of more than two tetrahedra by a single oxygen, aluminum is predominantly in tetrahedral coordination. Other Al-Si glasses which are richer in aluminum or which have non-bridging oxygens may contain Al tetrahedral triclusters, non-tetrahedral Al, or both. On the basis of distinctive 450–750 cm^?1 infrared bands, both silica and feldspar glasses resemble tridymite and related stuffed derivatives, not other crystalline silica polymorphs or feldspars. Either these glasses have a structure like that of tridymite on a local scale, or the disorder of the glasses causes drastic modification to the vibrations in question.     

Germanium-silicon fractionation in a tropical, granitic weathering environment

Germanium-silicon (Ge/Si) ratios were determined on quartz diorite bedrock, saprolite, soil, primary and secondary minerals, phytolith, soil and saprolite pore waters, and spring water and stream waters in an effort to understand Ge/Si fractionation during weathering of quartz diorite in the Rio Icacos watershed, Puerto Rico. The Ge/Si ratio of the bedrock is 2 μmol/mol, with individual primary mineral phases ranging between 0.5 and 7 μmol/mol. The ratios in the bulk saprolite are higher (∼3 μmol/mol) than values measured in the bedrock. The major saprolite secondary mineral, kaolinite, has Ge/Si ratios ranging between 4.8 and 6.1 μmol/mol. The high Ge/Si ratios in the saprolite are consistent with preferential incorporation of Ge during the precipitation of kaolinite. Bulk shallow soils have lower ratios (1.1-1.6 μmol/mol) primarily due to the residual accumulation of Ge-poor quartz.Ge/Si ratios measured on saprolite and soil pore waters reflect reactions that take place during mineral transformations at discrete depths. Spring water and baseflow stream waters have the lowest Ge/Si ratios (0.27-0.47 μmol/mol), reflecting deep initial weathering reactions resulting in the precipitation of Ge-enriched kaolinite at the saprolite-bedrock interface. Mass-balance calculations on saprolite require significant loss of Si and Al even within 1 m above the saprolite-bedrock interface. Higher pore water Ge/Si ratios (∼1.2 μmol/mol) are consistent with partial dissolution of this Ge-enriched kaolinite. Pore water Ge/Si ratios increase up through the saprolite and into the overlying soil, but never reach the high values predicted by mass balance, perhaps reflecting the influence of phytolith recycling in the shallow soil.     

Stoichiometry of smectite dissolution reaction

The dissolution stoichiometry of smectite-rich bentonites SAz-1, STx-1 and SWy-1 was studied at 50°C and pH 2 and 3 using flow-through reactors. In addition to smectite, these samples contain considerable amounts of silica phases (quartz, cristobalite and/or amorphous silica). As a result, the molar Al/Si ratios of the bulk samples are significantly lower than those of the pure smectite.Smectite dissolution was highly incongruent during the first few hundred to few thousand hours of the experiments. Release rates of Si, Mg, Ca and Na underwent a distinct transition from an initial period of rapid release to significantly lower release rate at steady state. A reversed trend was observed for release of Al, which gradually increased from very low starting release rate to higher release rate at steady state. At steady state the ratio of released Al to released Si was found to be constant and independent of the experimental conditions. We suggest that this ratio represents the Al/Si ratio of the smectite itself, and it is not influenced by the presence of accessory phases in the sample.The rapid release of calcium, sodium and magnesium from the interlayer sites is explained by ion-exchange reactions, whereas the fast release of silicon is explained by dissolution of amorphous silica. We interpret the initial slow release of Al as the result of inhibition of smectite dissolution due to coating or cementation of the smectite aggregates by amorphous silica. As the silica is dissolved, the aggregates fall apart and more smectite surfaces are exposed, resulting in an increase in the smectite dissolution rate. Thereafter, the system approaches steady state, in which the major tetrahedral and octahedral cations of smectite are released congruently.     

The glauconite–Fe‐illite–Fe‐smectite problem: a critical review

Iron silicate minerals are a significant component of sedimentary systems but their modes of formation remain controversial. Our analysis of published data identifies end‐member compositions and mixtures and allows us to recognize controls of formation of different mineral species. The compositional fields of glaucony, Fe‐illite, Fe–Al smectites are determined in the M⁺/4Si vs. Fe/Sum of octahedral cations (M⁺ = interlayer charge). Solid solutions could exist between these phases. The Fe–Al and Fe‐rich clay minerals form two distinct solid solutions. The earliest phases to be formed are Fe–Al smectites or berthierine depending on the sedimentation rate. Reductive microsystems appear in the vicinity of organic debris in unconsolidated sediments. The Fe is incorporated first in pyrite and then in silicates after oxidation. Potassium ions diffuse from the sea‐water–sediment interface. If not interrupted, the diffusion process is active until reaction completion is reached, i.e. formation of Fe‐illite or glauconite or a mineral assemblage (berthierine–nontronite) according to the available Al ion amounts in the microsystem. Mixed‐layer minerals are formed when the diffusion process is interrupted because of sedimentation, compaction or cementation. Despite the common belief of their value as palaeoenvironment indicators, these minerals can form in a variety of environments and over a period of millions of years during sediment burial.     

A review of the synthesis and characterisation of pillared clays and related porous materials for cracking of vegetable oils to produce biofuels

This paper presents an overview of the modification of clay minerals by propping apart the clay layers with an inorganic complex. This expanded material is converted into a permanent two-dimensional structure, known as pillared clay or shortly PILC, by thermal treatment. The resulting material exhibits a two-dimensional porous structure with acidic properties comparable to that of zeolites. Synthetic as well as natural smectites serve as precursors for the synthesis of Al, Zr, Ti, Fe, Cr, Ga, V, Si and other pillared clays as well as mixed Fe/Al, Ga/Al, Si/Al, Zr/Al and other mixed metal pillared clays. Biofuels form an interesting renewable energy source, where these porous, catalytically active materials can play an important role in the conversion of vegetable oils, such as canola oil, into biodiesel. Transesterification of vegetable oil is currently the method of choice for conversion to biofuel. The second part of this review focuses on the catalysts and cracking reaction conditions used for the production of biofuel. A distinction has been made in three different vegetable oils as starting materials: canola oil, palm oil and sunflower oil.     

Application of infrared spectroscopy to studies of silicate glass structure: Examples from the melilite glasses and the systems Na2O-SiO2 and Na2O-Al2O3-SiO2

Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO₄ tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm^?1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm^?1 is indicative of network-substituted AlO₄ polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm^?1 is shown to be associated with AlO₆ polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.     

Impacts of grain size sorting and chemical weathering on the geochemistry of Jingyuan loess in the northwestern Chinese Loess Plateau

Major and trace elemental compositions of loess samples collected from the Jingyuan section in the northwestern Chinese Loess Plateau (CLP) were analyzed to investigate the potential impacts of grain size sorting and chemical weathering on the loess geochemistry and to extract appropriate geochemical indices for better evaluating the East Asian monsoon variability. Based on variations of major and trace elements in different grain size fractions, seventeen elements were classified into three types: (1) Si and Na display higher contents with the increased particle sizes; (2) Al, Fe, Mg, K, Mn, Zn, Rb, Cr, V are mainly enriched in fine size fractions; (3) Ti, Ba, Zr, P, Ca and Sr show irregular variations among different size fractions. Comparison of Al-normalized elemental ratios with Zr/Rb and Rb/Sr ratios (two commonly employed indicators for grain size sorting and pedogenic weathering) indicates that Si/Al, Zr/Al, Ti/Al variations match well with Zr/Rb and grain size results, whilst Ca/Al, Sr/Al, P/Al ratios display similar variability as that of Rb/Sr ratio. Comparison of loess based proxies (e.g., elemental ratios, magnetic susceptibility, grain size) of Jingyuan section with speleothem and ice-core records confirms that elemental ratios of high-resolution loess sequences developed in the northwestern CLP can be employed to address fluctuations of the winter monsoon-induced grain size sorting and summer monsoon-related weathering and pedogenesis at glacial–interglacial and millennial timescales.     

滇东南弗拉斯期放射虫硅质岩地球化学特征及沉积环境探讨

在滇东南麻栗坡地区广泛分布的榴江组薄层状硅质岩中.发现包含放射虫动物群Helenifor robustum和Heleniore laticlavium的重要分子,地质时代为晚泥盆世弗拉斯早期.硅质岩SiO2含量在80.2%-95.72%之间,Al2O3含量集中在0.32%-3.83%之间,平均为2.07%,Si/Al值...     

Mechanical Behavior and Sulfate Resistance of Alkali Activated Stabilized Clayey Soil

Clayey subgrade soil requires treatment in order to make the subgrade stable for pavement structures. Treatment of clayey soil i.e. stabilization of clayey soil by cement, lime, and fly ash are established techniques used in geotechnical and highway engineering. Stabilization by alkali activation of fly ash is reported recently but literatures are limited. Present study investigates the stress strain behavior, peak stress and ultimate strain of clayey soil stabilized by slag and slag-fly ash blending by alkali activation. The peak stress as high as 25.0 N/mm² may be obtained at 50% slags content when 12 molar sodium hydroxide solutions were used. Peak stress, ultimate strain and slope of stress–strain curve of stabilized clay are controlled by Na/Al and Si/Al ratios. Stress–strain response and peak stress of slag and fly ash blended specimen are not governed by Na/Al and Si/Al ratios; rather the behavior is dependent predominantly on slag content.     

Germanium-silicon fractionation in the weathering environment

We present a detailed study of germanium behavior in the soil weathering environment as an important step toward using the Ge/Si system as a tracer of silicate weathering processes in both modern and ancient environments. Intensely weathered soils developed on Hawaiian basalts have bulk soil Ge/Si ratios 2 to 10 times higher than fresh basalt (e.g., 10 to 25 μmol/mol vs. 2.5 μmol/mol). Soil Ge concentrations increase with Si, and decrease with Fe, suggesting that Ge sequestration is related to accumulation of secondary soil silicates, rather than retention in soil Fe oxy-hydroxides. Sequential extractions of these soils suggest that Ge/Si fractionation takes place by Ge sequestration during the initial precipitation of secondary soil aluminosilicates (principally allophane). Further Si loss and changes in mineralogy as these soils age result in little additional Ge/Si fractionation. Ge/Si ratios in granitic soils and saprolites are strongly influenced by relative weathering rates of primary minerals. Kaolinite has a Ge/Si ratio (5.9 μmol/mol) higher than the plagioclase from which it forms (3.1 μmol/mol), whereas accumulation of primary quartz (Ge/Si 0.5 μmol/mol) prevents granitic soils from attaining high Ge/Si ratios. Laboratory synthesis of allophane confirms that Ge is preferentially partitioned into the solid phase upon precipitation of secondary aluminosilicates from solution.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—III. Local silicon environments and internal nucleation in silicate glasses

The local, up to second nearest neighbor, around Si atoms in alkali and alkaline earth-silicate glasses has been characterized by SiKβ X-ray emission spectroscopy. Principally two types of Si atoms can be distinguished. These are Si atoms with only other Si atoms as second nearest neighbours, and those with one or more alkali or alkaline earth atoms in their second coordination sphere. The spectroscopic results indicate that the lower molecular weight alkali and alkaline earth-silicate glasses tend towards a bimodal distribution of local Si environments, which is designated Q₄-Q₀ following the assignment by Engelhardtet al. (1975) for silica species in aqueous solutions. From a different perspective the outcome of these experiments suggests that, though the concentration of bridging oxygens (O(br)) and non-bridging oxygens (O(nbr)) is fixed by the stoichiometry of the glass, the distribution of O(nbr) in the glass varies according to the kind of alkali or alkaline earth atom present. From observed nucleation data on R₂O-SiO₂ (R = Li, Na, K) glasses it is inferred that a bimodal Q distribution and in particular the presence of Q₀ species dominates the internal nucleation process in the alkali and alkaline earth-silicate glasses studied. Using this inference rationalizations can readily be found to explain the observed resistance to thermal shock and devitrification rates of these glasses.     

Tracing mechanisms controlling the release of dissolved silicon in forest soil solutions using Si isotopes and Ge/Si ratios

The terrestrial biogenic Si (BSi) pool in the soil-plant system is ubiquitous and substantial, likely impacting the land-ocean transfer of dissolved Si (DSi). Here, we consider the mechanisms controlling DSi in forest soil in a temperate granitic ecosystem that would differ from previous works mostly focused on tropical environments. This study aims at tracing the source of DSi in forest floor leachates and in soil solutions under various tree species at homogeneous soil and climate conditions, using stable Si isotopes and Ge/Si ratios. Relative to granitic bedrock, clays minerals were enriched in ²⁸Si and had high Ge/Si ratios, while BSi from phytoliths was also enriched in ²⁸Si, but had a low Ge/Si ratio. Such a contrast is useful to infer the relative contribution of silicate weathering and BSi dissolution in the shallow soil on the release of DSi in forest floor leachate solutions. The δ³⁰Si values in forest floor leachates (−1.38‰ to −2.05‰) are the lightest ever found in natural waters, and Ge/Si ratios are higher in forest floor leachates relative to soil solution. These results suggest dissolution of ²⁸Si and Ge-enriched secondary clay minerals incorporated by bioturbation in organic-rich horizons in combination with an isotopic fractionation releasing preferentially light Si isotopes during this dissolution process. Ge/Si ratios in soil solutions are governed by incongruent weathering of primary minerals and neoformation of secondary clays minerals. Tree species influence Si-isotopic compositions and Ge/Si ratios in forest floor leachates through differing incorporation of minerals in organic horizons by bioturbation and, to a lesser extent, through differing Si recycling.     

Solubility mechanisms of fluorine in peralkaline and meta-aluminous silicate glasses and in melts to magmatic temperatures

Structural interaction between dissolved fluorine and silicate glass (25°C) and melt (to 1400°C) has been examined with ¹⁹F and ²⁹Si MAS NMR and with Raman spectroscopy in the system Na₂O-Al₂O₃-SiO₂ as a function of Al₂O₃ content. Approximately 3 mol.% F calculated as NaF dissolved in these glasses and melts. From ¹⁹F NMR spectroscopy, four different fluoride complexes were identified. These are (1) Na-F complexes (NF), (2) Na-Al-F complexes with Al in 4-fold coordination (NAF), (3) Na-Al-F complexes with Al in 6-fold coordination with F (CF), and (4) Al-F complexes with Al in 6-fold, and possibly also 4-fold coordination (TF). The latter three types of complexes may be linked to the aluminosilicate network via Al-O-Si bridges.The abundance of sodium fluoride complexes (NF) decreases with increasing Al/(Al + Si) of the glasses and melts. The NF complexes were not detected in meta-aluminosilicate glasses and melts. The NAF, CF, and TF complexes coexist in peralkaline and meta-aluminosilicate glasses and melts.From ²⁹Si-NMR spectra of glasses and Raman spectra of glasses and melts, the silicate structure of Al-free and Al-poor compositions becomes polymerized by dissolution of F because NF complexes scavenge network-modifying Na from the silicate. Solution of F in Al-rich peralkaline and meta-aluminous glasses and melts results in Al-F bonding and aluminosilicate depolymerization.Temperature (above that of the glass transition) affects the Qⁿ-speciation reaction in the melts, 2Q³ ⇔ Q⁴ + Q², in a manner similar to other alkali silicate and alkali aluminosilicate melts. Dissolved F at the concentration level used in this study does not affect the temperature-dependence of this speciation reaction.     

Electronic structure of spinel

The fundamental band gap between conduction and valence bands in aluminate spinels has been found to be at least 8·1 eV; the optical reflectivity peak at this energy possibly represents the lowest-energy exciton. In crystals with non-stoichiometric Al/Mg ratios, the intensity of this first reflection peak appears to decrease with increasing Al/Mg ratio; however, the peak energies themselves are essentially independent of stoichiometry. It seems likely that spinel and olivine in spinel-structure will have electronic transport behavior similar to that of olivine in its normal structure.     

Germanium/silica ratios in diagenetic chert nodules from the Ediacaran Doushantuo Formation,South China

Germanium/silica (Ge/Si) ratios of dolostone- and mudstone-hosted chert nodules from the Ediacaran (635–542 Ma) Doushantuo Formation in the Yangtze Gorges area, South China, are reported. These chert nodules typically have a calcite rim, a pyrite rim, and a silica core, the latter sometimes containing disseminated pyrite. The silica core was precipitated by early diagenetic replacement of carbonate and silty/muddy sediments. Two types of chert nodules are identified based on their mineralogy and geochemistry. Type-1 chert nodules are poor in disseminated pyrite in the silica core. They also have low Al, and show a strong positive correlation between Al contents and Ge/Si with a near-zero or negative intercept. In contrast, Type-2 chert nodules contain abundant disseminated pyrite in the silica core and show a weakly positive correlation between Ge/Si ratios and Al contents (with a large positive intercept on the Ge/Si axis). The Ge/Si of Doushantuo nodules are greater than those of Cretaceous deep-sea cherts, suggesting that the Ge/Si ratio of Ediacaran seawater/porewater was greater than the Cretaceous due to the more effective discrimination against Ge by inorganic opal precipitation relative to biogenic opal precipitation. The positive correlation between Ge/Si and Al can be interpreted using a mixing model with a pure chert (characterized by a low Ge/Si ratio) and an Al-rich endmember (characterized by a high Ge/Si ratio). The latter is most likely represented by a clay component, but the model-based estimate of the Ge/Si ratio inferred for the Al-rich (clay) endmember is much higher than that of Phanerozoic clay minerals. These high Ge/Si ratios for the clay endmember may be related to the generally high Ge/Si ratio of Ediacaran seawater, but could also be related to clay–organic matter interactions. Organic matter absorbed to clays could provide an additional source of Ge because certain organic molecules are known to have a high affinity for Ge due to their strong metal ion-chelating properties. The high Ge/Si ratio of the Al-rich endmember in Type-1 chert nodules suggests that Ge in porewaters from which these cherts precipitated may have been dominated by Ge–organic complexes. The low Ge/Si ratio inferred for the Al-rich endmember in Type-2 chert nodules is therefore taken to indicate that Ge was released from organic matter, perhaps due to anaerobic degradation of organic matter (accompanied by the formation of pyrite), and was redistributed between clay–organic endmembers and pure chert, resulting in a non-zero intercept in the Ge/Si vs. Al₂O₃ plots. These observations suggest that a strong terrestrial influence in a restricted sedimentary basin or a high content of dissolved organic carbon in Ediacaran seawater and porewater may have contributed to the dominance of Ge–organic complexes in the Doushantuo basin in the Yangtze Gorges area.     

Mineralogical–Geochemical Features of Ice-Rafted Sediments in Some Arctic Regions

The quantitative mineral composition estimated using the Rietveld method and some geochemical features are considered for bulk samples of the ice-rafted sediments (IRS) from some Arctic regions. Layer silicates in the studied samples vary from ~20 to ~50%. They are dominated by micas and their decomposition products (illite and likely some part of smectites) at significant contents of kaolinite, chlorite, and transformation/decomposition products of the latter. A significant content of illite and muscovite among layer silicates in most IRS samples suggests that sources of the sedimentary material were mainly mineralogically similar to modern bottom sediments of the East Siberian and Chukchi seas, as well as presumably sediments of the eastern Laptev Sea. It is suggested that a significant kaolinite fraction in IRS samples from the North Pole area can be caused by the influx of ice-rafted fine-grained sedimentary material from the Beaufort or Chukchi seas, where kaolinite is supplied from the Bering Sea. Positions of IRS data points in the (La/Yb)_N–Eu/Eu*, (La/Yb)_N–(Eu/Sm)_N, and (La/Yb)_N–Th diagrams show that the studied samples contain variable proportions of erosion products of both mafic and felsic magmatic rocks and/or sufficiently mature sedimentary rocks. This conclusion is confirmed by localization of IRS data points in the Th/Co–La, Si/Al–Ce, and Si/Al–Sr diagrams.     

Isotopic fractionation of iron, potassium, and oxygen in stony cosmic spherules: Implications for heating histories and sources

Atmospheric heating alters the compositions and textures of micrometeorites. To understand the changes and to test a proposed relationship between a micrometeorite’s petrographic texture and its degree of heating, we made elemental and multiple isotope analyses of stony cosmic spherules (sCS) collected from the South Pole Water well. Specifically, we analyzed the elemental compositions of 94 sCS and the isotopic ratios of Fe, K and O, on 43, 12 and 8 of these sCS, respectively.Our results show that sCS classified as strongly heated generally have lower concentrations of volatile and moderately volatile elements. Of the 43 spherules analyzed for Fe isotopes, only 5 have δ⁵⁷Fe >5‰. In contrast, enrichment of ⁴¹K is pervasive (δ⁴¹K >0 in all 12 spherules analyzed) and large (up to 183‰). The determination of K isotope abundances in sCS may therefore be useful in deciphering thermal histories. Three of the eight sCS analyzed for O isotopes are mass fractionated with δ¹⁸O >30‰. We attribute two of these three δ¹⁸O enrichments to evaporative losses of oxygen in the atmosphere and the third to the presence in the parent material of an exotic phase, perhaps a sulfate or a carbonate. The K isotope and O isotope data are broadly consistent with the proposed textural classification.Because most spherules were not heated enough to fractionate Al, Mg, or Si, we compared the measured Mg/Al and Si/Al ratios directly to those of conventional meteorites and their matrices. ∼30% of the sCS have compositions outside the range defined by the bulk and the matrix compositions of known meteorite groups but consistent with those of pyroxene- and olivine-rich materials and may be samples of chondrules. The other 70% have Mg/Al and Si/Al ratios similar to those of CI, CM, CO, and CV chondrites. Natural variability of the Mg/Al and Si/Al ratios precludes the assignment of an individual sCS to a particular class of C-chondrite.     

Al environment in tectosilicate and peraluminous glasses: A Al MQ-MAS NMR, Raman, and XANES investigation

Tecto-aluminosilicate and peraluminous glasses have been prepared by conventional and laser heating techniques, respectively, in the CaO-Al₂O₃-SiO₂ system. The structure of these glasses were studied using Raman spectroscopy, X-ray absorption at the Al K-edge and ²⁷Al NMR spectroscopy with two different high fields (400 and 750 MHz). Raman spectroscopy and X-ray absorption are techniques sensitive to the network polymerization and, in particular, show different signal as a function of silica content. However, these two techniques are less sensitive than NMR to describe the local aluminium environment. For tectosilicate glasses, aluminium in five-fold coordination, ^[5]Al, was found and a careful quantification allows the determination of a significant amount of ^[5]Al (7% in the anorthite glass). The proportion of ^[5]Al increases for the peraluminous glasses with small amounts (<2%) of six-fold coordination, ^[6]Al. The presence of ^[5]Al agrees with previous observations of the existence of nonbridging oxygens (NBOs) in tectosilicate compositions. However, the proportion of ^[5]Al in the present study indicates that no major proportion of triclusters (oxygen coordinated to three (Si,Al)O₄ tetrahedra) is required to explain these NBOS.