Lightning-strike fusion of gabbro and formation of magnetite-bearing fulgurite, Cornone di Blumone, Adamello, Western Alps, Italy

The Adamello gabbro exposed on the summit of Cornone di Blumone, Western Alps, Italy, has been fused by lightning strikes to form magnetite-rich fulgurites produced by melting of magnetite, hornblende, calcic plagioclase and minor clinopyroxene. The composition of quench magnetite in the fulgurite is 44.4 Fe₃O₄; 27.5 MgFe₂O₄; 15.1 FeAl₂O₄; 7.9 Fe₂TiO₄; 2.5 Fe₂SiO₄; 1.9 CaFe₂O₄; 0.8 MnFe₂O₄ and is inferred to have crystallized from a low-Si, Fe-rich melt under high oxidation conditions of about 1 log unit below the log₁₀?O₂ of hematite–magnetite. The low Si, Fe-rich melt is considered to have been produced from fusion of magnetite + hornblende-rich areas of the host gabbro and/or possible separation of an immiscible high Fe₂O₃/FeO Fe-rich, low-Si melt from a more siliceous glass during superheating. Skeletal-dendritic morphologies of magnetite in the fulgurite indicate crystallization under conditions of extreme supercooling. Juxtaposition of areas exhibiting different growth habits and crystal sizes of magnetite may reflect compositionally different local melt domains and/or small differences in the delicate balance between nucleation and growth in domains that had slightly different, although ultrafast, cooling rates.     

Fulgurites: lightning strikes providing unique clues to palaeoenvironments

Strange in appearance and unique in origin, fulgurites are named for the Latin word for lightning. They are formed when lightning strikes rocks or sand that contains silica. They can form remarkably quickly… seconds as opposed to years or millennia. That in itself makes them remarkable, but they have other unusual qualities that make them even more amazing. Some hold ancient air within that can offer a window into past environments.     

A geochemical approach to constraining the formation of glassy fallout debris from nuclear tests

Glassy nuclear fallout debris from near-surface nuclear tests is fundamentally reprocessed earth material. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. This study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclear test (“trinitite”) and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. The volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.     

Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts

The coordination environment of Fe(II) has been examined in seven anhydrous ferrosilicate glasses at 298 K and 1 bar using ⁵⁷Fe Mössbauer, Fe K-edge X-ray near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS), UV-Vis-NIR, and magnetic circular dichroism (MCD) spectroscopies. Glasses of the following compositions were synthesized from oxide melts (abbreviation and nonbridging oxygen:tetrahedral cation ratio (NBO/T) in parentheses): Li₂FeSi₃O₈ (LI2: 1.33), Rb₂FeSi₃O₈ (RB2: 1.33), Na_l.08Fe_l.l7Si_3.l3O₈ (NAl: 1.09), Na_l.46Ca_0.24Fe_l.08Si_2.97O₈ (NC6: 1.38), Na_l.09Ca_0.51Fe_0.72Si_3.10O₈ (NC2: 1.15), Na_0.99Ca_0.92Fe_0.24 Si_3.17O₈ (NCl: 1.04), and Na_0.29Mg_0.53Ca_0.52Fe_0.56Al_0.91Si_2.44O₈ (BAS: 1.05). Mössbauer, XANES, and EXAFS information suggests that iron is dominantly ferrous in all glasses (<10 atom% Fe(III)) with an average first-neighbor Fe(II) coordination varying from ∼ 4 to 5.2 (±0.2) oxygens. The UV-Vis-NIR spectrum of each sample exhibits intense absorption centered near 8100-9200 cm⁻¹ and weak absorption near 5000 cm^−l, which cannot be assigned unambiguously. The MCD spectrum of NC6 glass, which is the first such measurement on a silicate glass, shows three transitions at ∼8500 cm⁻¹, ∼6700 cm⁻¹, and ∼4500 cm⁻¹. The behavior of these MCD bands as a function of temperature (1.6 K to 300 K) and magnetic field strength (1 T to 7 T) indicates that they most likely arise from three distinct Fe(II) sites with different ground states, two of which are 5-coordinated and one of which is 4-coordinated by oxygens.The combined results suggest that Fe(II) predominantly occupies 5- and 4-coordinated sites in each glass, with the ratios differing for the different compositions. Small amounts of 6-coordinated Fe(II) are possible as well, but primarily in the more basic glass compositions such as BAS. The substitution of Li(I) for Rb(I) in the M₂FeSi₃O₈ base glass composition causes a weakening of the average Fe(II)-O bond, as indicated by the longer Fe(II)-O distance in the latter. The basalt composition glass was found to have the largest Fe(II) sites relative to those in the other glasses in this study. A bond valence model that helps predict the coordination number of Fe(II) in silicate glasses is proposed. The structural information extrapolated to Fe(II)-bearing melts is parameterized using bond valence theory, which helps to rationalize the melt-crystal partitioning behavior of ferrous iron in natural and synthetic melt-crystal systems.     

Petrographic and geochemical analysis of caliche profiles in a Bahamian Pleistocene dune

Two caliche profiles from a Pleistocene carbonate dune on San Salvador Island, Bahamas, were examined by petrographic and geochemical analysis. Profile A is an immature buried caliche profile characterized by caliche pisolites, a friable crust and abundant Cerion. Profile B is a more well-developed caliche profile at the top of the dune which contains abundant pisolites, rhizomorphs, laminated calcrete, a breccia and abundant Cerion. Geochemical changes in caliche profiles relative to the host rock are an increase in Al₂O₃, Fe₂O₃ and total organic carbon, a decrease in Mg and Sr, and a decrease in δ¹³C_carb, δ¹⁸O_carb and δ13C_org. The magnitude of these changes is probably a function of the duration of subaerial exposure and resultant colonization by dune plants and associated microflora. Abundance of calcified filaments and needle-fibre crystals in profile A attests to the importance of microbial processes in the early development of caliche profiles. Biogenic structures are largely destroyed in profile B due to recrystallization, but indirect evidence of biological activity is retained in the form of carbon isotope values.     

Application of Glauconite Sedimentary Geochronology

Glauconite is widely distributed in space and time.In China glauconite-bearing strata are extensive occurrence ranging from Late Cretaceous to Middle Proterozoic in age.X-ray powder analysis,X-ray diffracition analysis and differential thermal analysis revealed that glauconite has a mica-type structure between dioctahedron and trioctahedron.Its chemical composition is:Al2O310.6%,SiO249.23%,MgO3.24%,Fe2O317.40%,FeO1.8%,and K2O7.92%,Its crystal form and thermal properties are very similar to those of mica-like clay minerls.According to isotopic age determinations of glauconite in modern oceans (including the East China Sea,the South China Sea and the Yellow Sea),we consider that in the extreme case glauconite is an authigenic mineral.It is generally formed in sedimentary rocks.Is has further proved that glauconite can be used to determine the ages of sedimentary rocks.     

Experimental study of the bcc-fcc phase transformations in the Fe-rich system Fe-Si at high pressures

In situ X-ray diffraction experiments at high pressure were carried out up to 8.9 GPa and 1100 °C to study phase transformations of iron and two iron-silicon alloys Fe_0.91Si_0.09 and Fe_0.83Si_0.17. For iron, the transformation from the bcc phase to the fcc phase was observed at pressures 3.8–8.2 GPa and temperatures that are consistent with previous in situ X-ray diffraction studies. Reversal of the transformation of iron was found to be sensitive to temperature; hysteresis of the transformation increased from 25 °C at 3.8 GPa to 100 °C at 7.0 GPa, primarily because the bcc-fcc phase boundary has a negative Clayperon slope. In the binary system Fe-Si, the observations of the present study indicate that the ferrite (bcc phase)-stabilizing behavior of silicon persists at high pressures and that the maximum solubility of silicon in the fcc phase increases with increasing pressure: (1) the transformation from the bcc phase to the fcc phase was observed in Fe_0.91Si_0.09 at 6.0, 7.4 and 8.9 GPa and the temperatures measured at the onset of the transformations were 300 °C higher than those in iron at similar pressures, (2) the transformation rate in Fe_0.91Si_0.09 was extremely sluggish compared to that of iron, and (3) the bcc-fcc phase transformation was not observed in Fe_0.91Si_0.09 at 4.7 GPa up to 1000 °C and in Fe_0.83Si_0.17 at 8.2 GPa and 1100 °C. Received: 1 June 1998 / Revised, accepted: 9 October 1998     

Compositional variation and primary water contents of differentiated interstitial and included glasses in boninites

 Interstitial glasses and glasses in small inclusions in Mg-rich phenocrysts of 14 boninites from New Caledonia, the Mariana Trench, Cape Vogel and Chichi-jima were analysed by electron microprobe and the water contents measured in situ by ion microprobe. The glasses are remarkably fresh and abundant (∼30–90 vol.%), and the phenocrysts are often skeletal with glass inclusions. Broad-beam analyses (∼1030) of interstitial glasses and ∼180 point analyses of glass inclusions were carried out, as well as ∼100 hydrogen analyses. Most glasses have low water-free totals, high water contents, very low MgO, and low total iron; they are almost entirely quartzofeldspathic and with few exceptions (Q+or+ab+ an+C) lies in the range 83–96. The interstitial glasses from New Caledonia, the Marianas and most of the glasses from Chichi-jima are dacitic, those from Cape Vogel straddle dacitic and andesitic compositions, whereas the glasses in a highly glassy sample from Chichi-jima are high-Mg andesitic or boninitic with up ∼9 wt% MgO, and are, with the exception of a few high-Ca boninites from Tonga, the most Mg-rich interstitial glasses so far described in boninites. Glasses included in orthopyroxene, olivine or clinoenstatite are boninitic or high-Mg andesitic in the highly glassy rock and dacitic to high-silica dacitic in the others. They are in general slightly more differentiated than the interstitial glasses, because of more-extensive crystallization on the host crystal in small inclusions. The interstitial glass compositions show a direct relationship between silica and Al₂O₃ and, for most glasses, alkalis, and inverse relationships between silica and CaO, FeO and MgO; alkalis and TiO₂ show, however, a broad spread in values in glasses from the Marianas and New Caledonia. Included glasses show similar variations. Water contents in interstitial glasses are ∼2 wt% for the highly glassy high-Mg andesitic glasses from Chichi-jima, ∼5.4 wt% for the more differentiated andesitic to dacitic glasses from Cape Vogel, and ∼6.7–7.0 wt% in the most differentiated dacitic ones from the Marianas and New Caledonia. Water contents in glass inclusions in olivine, orthopyroxene and clinoenstatite are in the range ∼1.9–3.3 wt%. The interstitial glasses are black and not vesicular, showing that the liquids did not reach supersaturation after eruption on or intrusion near the sea floor, or were insufficiently so to allow nucleation of water vapour bubbles. The water is inferred to be primary and to increase strongly with crystallization in the residual liquid down to the glass-transition T. Received: 19 December 1994 / Accepted: 5 October 1995     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—V. The polymeric structure of silica in albite and anorthite composition glass and the devitrification of amorphous anorthite

²⁹Si MAS NMR experiments have been carried out to determine the silica species distribution (Q distribution) in albite, NaAlSi₃O₈, and anorthite, CaAl₂Si₂O₈, composition glasses (designated albite and anorthite glass). Our results indicate that the Q distribution of albite glass contains all five possible silica species and shows a tendency towards high Q₃ and Q₄ concentrations, whereas anorthite glass does not contain Q₄ and has a high Q₀ concentration. Rationalizations are made in terms of the observed Q distributions to explain differences in devitrification behavior of these two glasses. ²⁷Al MAS NMR data for these glasses suggest that differences in devitrification behavior between these two glasses should be ascribed to small growth rates rather than small nucleation rates of crystalline albite from albite glass.     

Polarized single crystal absorption spectroscopy of the Pnam-P2 1/a transition of Ilvaite Ca(Fe2+, Fe3+)Fe2+Si2O8(OH) as measured between 300 K and 450 K

The temperature dependence of the absorption spectra of ilvaite, Ca(Fe²⁺,Fe³⁺)Fe²⁺Si₂O₈(OH), shows strongly one dimensional transport behaviour with no singularity at the Pnam-P2₁/a phase transition point near 335 K. Polarized single crystal transmission measurements were carried out between 300 K and 450 K in a frequency range between 600 and 23 000 cm⁻¹. No Drude —absorption at low energies was found at any temperature. A macroscopic, thermodynamic model based on Landau-Ginzburg theory is given which accounts for the observed macroscopic properties of the structural phase transition and its coupling with the Fe²⁺-Fe³⁺ ordering. This ordering scheme is discussed on an atomistic level and compared with the behaviour of magnetite and trans-(CH) _x .     

Shock wave-induced interaction between meteoritic iron and silicates

The possibility of shock wave-induced interaction between meteoritic iron was estimated based on the results of experiments on the shock wave loading of mixtures of kamacite from the Sikhote Alin iron meteorite with quartz, albite, oligoclase, enstatite, olivine, and serpentine. The experimental samples were then examined with the application of optical microscopy, microprobe analysis, and M?ssbauer spectroscopy. As a result of shock wave load, the metal was proved to become enriched in Si, while the quartz, albite, and oligoclase melted glasses acquired bivalent Fe ions. The products of our experiments with quartz and feldspar mixtures with kamacite were determined to contain paramagnetic metallic iron, and the surroundings of iron atoms in the silicate constituent of the olivine and enstatite mixtures with kamacite become locally more heterogeneous. Our results indicate that shock waves induce redox reactions between Fe and silicates according to the scheme 2Fe⁺² + Si⁺⁴ = 2Fe⁺² + Si⁰, where Fe⁰ and Si⁰ are iron and silicon in metal and Fe⁺² and Si⁺⁴ are iron and silicon in the sillimanite matrix.     

Electric conductivity of Fe2SiO4–Fe3O4 spinel solid solutions

 The spinel solid solution was found to exist in the whole range between Fe₃O₄ and γ-Fe₂SiO₄ at over 10 GPa. The resistivity of Fe_{3− x} Si _x O₄ (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe³⁺ and Fe²⁺ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe₂SiO₄ component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe³⁺–Fe²⁺ electron hopping with increasing the total Si content. This is probably because a large number of Si⁴⁺ ions occupies the octahedral site and the adjacent Fe²⁺ keeping the local electric neutrality around Si⁴⁺ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe₃O₄) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si⁴⁺ substitution. Received: 15 March 2000 / Accepted: 4 September 2000     

Structure of mineral glasses—I. The feldspar glasses NaAlSi3O8, KAlSi3O8, CaAl2Si2O8

The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO₂ glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO₂ glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results.     

Influence of composition and thermal history of volcanic glasses on water content as determined by micro-Raman spectrometry

Development of Raman spectrometry for quantification of water content in natural glasses requires the assessment of the dependence of the technique on glass composition and thermal history. In the low frequency domain, Raman spectra topology varies due to glass depolymerization and substitution in the framework of (Si⁴⁺)^IV by alkali-balanced (Al³⁺)^IV and (Fe³⁺)^IV in calcalkaline (rhyolite to basaltic andesite) and alkaline (trachyte, phonolite to alkali basalt) glasses. These processes result in strong dependence of previous analytical procedure (internal calibration) on glass composition. Here, we show that an analytical procedure based on calibration to an external standard is only faintly composition-dependent for Si-rich alkaline glasses (trachytes–phonolites). For a given glass composition, thermal history also plays a fundamental role in the choice of Raman procedure for water analysis. Repeated cycles of thermal annealing induce microcrystallization of hydrous trachyte glasses and modify cation distribution in the glass structure. Application of these concepts to analysis of banded obsidians suggests that small-scale heterogeneities in glasses are not simply related to magma degassing, but could depend on thermal history and consequent relaxation paths in the melt.     

Petrology, geochemistry, S, Cl and F abundances, and S oxidation state of sideromelane glass shards from Pleistocene ash layers north and south of Gran Canaria (ODP Leg 157)

Major elements, S, F, Cl concentrations and relative proportions of S⁶⁺ to total S were analyzed with electron microprobe in sideromelane glass shards from Pleistocene volcaniclastic sediments drilled during ODP Leg 157. Glasses are moderately to strongly evolved and represent a spectrum from alkali basalt, basanite and nephelinite through hawaiite, mugearite and tephrite to phonolitic tephrite. Measured S⁶⁺/ΣS (0.03–0.98) and calculated Fe²⁺/Fe³⁺ (2.5–5.8) ratios in the melt yield preeruptive redox conditions ranging from NNO−1.4 to NNO+2.1. The morphology of the glass shards, variations of S and Cl concentrations (0.010–0.127 wt% S, 0.018–0.129 wt% Cl), calculated preeruptive temperatures (1030–1200 °C) and oxygen fugacities suggest that glasses deposited even within the same ash layers have diverse origin and may have resulted from both submarine and subaerial eruptions. Most vesicle-free glasses are characterized by high concentrations of S and represent undegassed or slightly degassed submarine lavas, whereas vesiculated glasses with low concentrations of S and Cl are strongly degassed and can be ascribed to the eruptions in shallow water or on land. Sideromelane glass shards at Sites 953 are thought to have resulted from submarine eruptions northeast of Gran Canaria, glasses at Site 954 represent mostly volcaniclastic material of shallow water submarine and subaerial eruptions on Gran Canaria and Tenerife, and glasses deposited at Site 956 resulted from submarine or explosive eruptions on Tenerife. Received: 8 April 1997 / Accepted: 27 October 1997     

The soils on the calcareous sand dunes southeast of South Australia

 The properties of soils on previously dated sand dunes from Robe to Naracoorte in South Australia were examined. In these areas younger sand dunes are composed of fresh sand, but older sand dunes are composed of calcarenited sand. The soils on the sand dunes developed successionally by the age of sand dunes. The soil properties of these sand dunes differ depending on the ages of the sand dunes. The properties of sand particles in soils are as follows: (1) On the sand dunes of 4300 years B.P., A/C profile developed (Rendzina). On the sand dunes older than 125 000 years B.P. and on the plateau of Tertiary limestone, soil profiles of A₁/AB/B/C on the sand dunes of 83 000 years B.P. and A₁/A₃/B₁/B₂/C (Terra rossa) are well developed. (2) Within the sand of A/C horizons of the sand dunes with the age of 4300 year B.P., the calcite grain content is about 64%, and the quartz content is about 35%. Within the B horizons of soils on the dunes from 83 000 years B.P. to 347 000 years B.P., the calcite grain content is only 1–2%; however, the quartz grain content is about 92%. In the B₂ horizons of soils on the dune of 690 000 years B.P. and on the Tertiary plateau, there are some calcite grains but the quartz grain content is about 96%. (3) The average size of quartz grains in the soils on the sand dunes from 4300 B.P. to 347 000 years B.P. is generally smaller, but the average size of quartz on the sand dunes of 690 000 year B.P. becomes larger and the grains are well rounded. On the Tertiary limestone plateau, the average quartz size becomes again smaller, and the grains are more rounded. (4) Fe_t in B₂ horizon of the soil profiles increases clearly corresponding to the age. Iron activity expressed by Fe_o/Fe_d also shows a close relation to the chronological sequence. The B horizon of the soil profiles shows a drastic decrease of Fe_o/Fe_d according to the age. Iron crystalinity, (Fe_d-Fe_o)/Fe_t, has a tendency for a positive relation with increasing age. Received: 1 June 1995 · Accepted: 4 December 1995     

Transport properties of low-sanidine single-crystals, glasses and melts at high temperature

Thermal diffusivity (D) was measured using laser-flash analysis from oriented single-crystal low-sanidine (K_0.92Na_0.08Al_0.99Fe³⁺ _0.005Si_2.95O₈), and three glasses near KAlSi₃O₈. Viscosity measurements of the three supercooled liquids, in the range 10^6.8 to 10^12.3 Pa s, confirm near-Arrhenian behavior, varying subtly with composition. For crystal and glass, D decreases with T, approaching a constant near 1,000 K: D _sat ∼ 0.65 ± 0.3 mm² s⁻¹ for bulk crystal and ∼0.53 ± 0.03 mm² s⁻¹ for the glass. A rapid decrease near 1,400 K is consistent with crossing the glass transition. Melt behavior is approximated by D = 0.475 ± 0.01 mm² s⁻¹. Thermal conductivity (k _lat) of glass, calculated using previous heat capacity (C _P) and new density data, increases with T because C _P strongly increases with T. For melt, k _lat reaches a plateau near 1.45 W m⁻¹ K⁻¹, and is always below k _lat of the crystal. Melting of potassium feldspars impedes heat transport, providing positive thermal feedback that may promote further melting in continental crust.     

A crystallographic and m?ssbauer spectroscopy study of Fe

The crystal chemistry of garnet solid solutions on the Fe ₃ ²⁺ Al₂Si₃O₁₂-Fe ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂ (almandine-“skiagite”) and Ca₃Fe ₂ ³⁺ Si₃O₁₂-Fe ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂ (andradite-“skiagite”) joins have been investigated by single-crystal X-ray structure refinements and M?ssbauer spectroscopy. Together, these two solid solution series encompass the complete range in Fe³⁺/ΣFe from 0.0 to 1.0. All garnets are isotropic and were re0fined in the Ia d space group. Small excess volumes of mixing are observed in andradite-“skiagite” solid solutions (W _v =1.0±0.2 cm³ mol^-1) and along the almandine-“skiagite” join (W _v =-0.77±0.17cm³ mol^-1). The octahedral (Al, Fe³⁺)-O bond lengths show a much greater variation across the almandine-skiagite join compared to the andradite-skiagite garnets. The dodecahedral (X)-O bond lengths show the opposite behaviour. In andradite-“skiagite” solid solutions, the octahedral site passes from being flattened to elongated parallel to the 3 axis of symmetry with increasing “skiagite” content. A perfect octahedron occurs in a composition of ≈35 mol% “skiagite”. The occupancy of the neighboring dodecahedral sites has the greatest effect on octahedral distortion and vice versa. The M?ssbauer hyperfine parameters of Fe²⁺remain constant in both solid solutions. The hyperfine parameters of Fe³⁺ (at room temperature: centre shift=0.32–0.40 mm/sec, quadrupole splitting (QS)≈0.21–0.55 mm/ sec) indicate that all Fe³⁺ is in octahedral coordination. The Fe³⁺ parameters are nearly constant in almandine-“skiagite” solid solutions, but vary significantly across the andradite-“skiagite” join. The structural unit that contributes to the electric field gradient of the octahedral site is different from that of the coordinating oxygen polyhedron, probably involving the neighboring dodeca-hedral sites.     

Paragenesis of unusual Fe-cordierite (sekaninaite)-bearing paralava and clinker from the Kuznetsk coal basin,Siberia, Russia

Sekaninaite (X_Fe > 0.5)-bearing paralava and clinker are the products of ancient combustion metamorphism in the western part of the Kuznetsk coal basin, Siberia. The combustion metamorphic rocks typically occur as clinker beds and breccias consisting of vitrified sandstone–siltstone clinker fragments cemented by paralava, resulting from hanging-wall collapse above burning coal seams and quenching. Sekaninaite–Fe-cordierite (X_Fe = 95–45) is associated with tridymite, fayalite, magnetite, ± clinoferrosilite and ±mullite in paralava and with tridymite and mullite in clinker. Unmelted grains of detrital quartz occur in both rocks (<3 vol% in paralavas and up to 30 vol% in some clinkers). Compositionally variable siliceous, K-rich peraluminous glass is <30% in paralavas and up to 85% in clinkers. The paralavas resulted from extensive fusion of sandstone–siltstone (clinker), and sideritic/Fe-hydroxide material contained within them, with the proportion of clastic sediments ≫ ferruginous component. Calculated dry liquidus temperatures of the paralavas are 1,120–1,050°C and 920–1,050°C for clinkers, with calculated viscosities at liquidus temperatures of 10^1.6–7.0 and 10^7.0–9.8 Pa s, respectively. Dry liquidus temperatures of glass compositions range between 920 and 1,120°C (paralava) and 920–960°C (clinker), and viscosities at these temperatures are 10^9.7–5.5 and 10^8.8–9.7 Pa s, respectively. Compared with worldwide occurrences of cordierite–sekaninaite in pyrometamorphic rocks, sekaninaite occurs in rocks with X_Fe (mol% FeO/(FeO + MgO)) > 0.8; sekaninaite and Fe-cordierite occur in rocks with X_Fe 0.6–0.8, and cordierite (X_Fe < 0.5) is restricted to rocks with X_Fe < 0.6. The crystal-chemical formula of an anhydrous sekaninaite based on the refined structure is | \textK_0.02 |(\textFe_1.54^{2 +} \textMg_0.40 \textMn_0.06 )_{\Upsigma 2.00}^M [(\textAl_1.98 \textFe_0.02^{2 +} \textSi_1.00 )_{\Upsigma 3.00}^T1 (\textSi_3.94 \textAl_2.04 \textFe_0.02^{2 +} )_{\Upsigma 6.00}^T2 \textO₁₈ ]. \left| {{\text{K}}_{0.02} } \right|({\text{Fe}}_{1.54}^{2 + } {\text{Mg}}_{0.40} {\text{Mn}}_{0.06} )_{\Upsigma 2.00}^{M} [({\text{Al}}_{1.98} {\text{Fe}}_{0.02}^{2 + } {\text{Si}}_{1.00} )_{\Upsigma 3.00}^{T1} ({\text{Si}}_{3.94} {\text{Al}}_{2.04} {\text{Fe}}_{0.02}^{2 + } )_{\Upsigma 6.00}^{T2} {\text{O}}_{18} ].