Paleoenvironments and geochemistry across a continuous Permian–Triassic boundary section at B?kk Mountains,Hungary

The Bálvány North Permian-Triassic boundary sediments were deposited on a carbonate platform in the tropical part of the western Paleo Tethys ocean.The overall elemental geochemistry of the detailed two-metre-thick section across the boundary that we studied shows that the clastic content of the sediments came from dominantly silica-rich continental sources though with some more silica-poor inputs in the uppermost Permian and lowest Triassic limestones as shown by Ni/Al and Nb/Ta ratios.These inputs bracket, but do not coincide with, the main extinctions and associated C, O and S changes.Increased aridity at the Permian-Triassic boundary with increased wind abrasion of suitable Ti-bearing heavy minerals accounts for both the high Ti/Al and Ti/Zr ratios.Various geochemical redox proxies suggest mainly oxic depositional conditions, with episodes of anoxia, but with little systematic variation across the Permian–Triassic extinction boundary.The lack of consistent element geochemical changes across the Permian-Triassic boundary occur not only in adjacent shallower-water marine sections, and in other marine sections along the SW Tethys margin such as the Salt Range sections in Pakistan, but also in deeper shelf and oceanic sections, and in non-marine African and European continental sediments.In the absence of significant changes in physical environments, chemical changes in the atmosphere and oceans,reflected in various isotopic changes, drove the Permian–Triassic extinctions.     

Effects of the degree of polymerization on the structure of sodium silicate and aluminosilicate glasses and melts: An O NMR study

Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report ¹⁷O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na₂O/SiO₂ ratio and Na₂O/Al₂O₃ ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na₂O-k(SiO₂)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na₂O/SiO₂ ratio (k), as predicted from the composition. The ¹⁷O isotropic chemical shifts (¹⁷O δ_iso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO₂ content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO₂ content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO₂ content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na₂O]_x[Al₂O₃]_1−xSiO₂, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al₂O₃ content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al₂O₃ content at a constant mole fraction of SiO₂. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO₂.     

The global oscillation network group site survey

The Global Oscillation Network Group (GONG) Project is planning to place a set of instruments around the world to observe solar oscillations as continuously as possible for at last three years. The Project has now chosen the sites that will comprise the network. This paper describes the methods of data collection and analysis that were used to make this decision.Solar irradiance data were collected with a one-minute cadence at fifteen sites around the world and analyzed to produce statistics of cloud cover, atmospheric extinction, and transparency power spectra at the individual sites. Nearly 200 reasonable six-site networks were assembled from the individual stations, and a set of statistical measures of the performance of the networks was analyzed using a principal component analysis. An accompanying paper presents the results of the survey.     

The measurement of long-period oscillations at Sacramento Peak Observatory and South Pole

A program to measure long-period brightness oscillations at the solar limb has been pursued at Sacramento Peak Observatory for several years. Past improvements in observing technique and data analysis are reviewed. The encouraging results aid in the verification of the reality and the origin of oscillatory signals. However, the main stumbling block to this and other observational programs is the length of observing sequences imposed by the day/night cycle. The South Pole has received considerable attention as a site where extended observations might be possible. Currently, the Sacramento Peak program is developing a South Pole telescope designed for the observing technique and data analysis proven in Sunspot. A review of pertinent South Pole site parameters is given here for other workers who may be considering South Pole observations. Observing sequences longer than 150 hr are possible, though rare. Data sets of this duration are very attractive for solar oscillation studies.Proceedings of the 66th IAU Colloquium: Problems in Solar and Stellar Oscillations, held at the Crimean Astrophysical Observatory, U.S.S.R., 1–5 September, 1981.Operated by the Association of Universities for Research in Astronomy, Inc., under contract AST 78-17292 with the National Science Foundation.Summer Research Assistant at Sacramento Peak Observatory.     

Dynamics of the α-β phase transitions in quartz and cristobalite as observed by in-situ high temperature 29Si and 17O NMR

Relaxation times (T₁) and lineshapes were examined as a function of temperature through the - transition for ²⁹Si in a single crystal of amethyst, and for ²⁹Si and ¹⁷O in cristobalite powders. For single crystal quartz, the three ²⁹Si peaks observed at room temperature, representing each of the three differently oriented SiO₄ tetrahedra in the unit cell, coalesce with increasing temperature such that at the - transition only one peak is observed. ²⁹Si T₁'s decrease with increasing temperature up to the transition, above which they remain constant. Although these results are not uniquely interpretable, hopping between the Dauphiné twin related configurations, ₁ and ₂, may be the fluctuations responsible for both effects. This exchange becomes observable up to 150° C below the transition, and persists above the transition, resulting in -quartz being a time and space average of ₁ and ₂. ²⁹Si T₁'s for isotopically enriched powdered cristobalite show much the same behavior as observed for quartz. In addition, ¹⁷O T₁'s decrease slowly up to the - transition at which point there is an abrupt 1.5 order of magnitude drop. Fitting of static powder ¹⁷O spectra for cristobalite gives an asymmetry parameter () of 0.125 at room T, which decreases to <0.040 at=" the=" transition=" temperature.=" the=" electric=" field=" gradient=" (efg)=" and=" chemical=" shift=" anisotropy=" (csa),=" however,=" remain=" the=" same,=" suggesting=" that=" the=" decrease=" in="> is caused by a dynamical rotation of the tetrahedra below the transition. Thus, the mechanisms of the - phase transitions in quartz and cristobalite are similar: there appears to be some fluctuation of the tetrahedra between twin-related orientations below the transition temperature, and the -phase is characterized by a dynamical average of the twin domains on a unit cell scale.     

A new method of measuring the cluster peculiar velocity power spectrum

We propose to use spatial correlations of the kinetic Sunyaev–Zeldovich (KSZ) flux as an estimator of the peculiar velocity power spectrum. In contrast with conventional techniques, our new method does not require measurements of the thermal SZ signal or the X-ray temperature. Moreover, this method has the special advantage that the expected systematic errors are always subdominant to statistical errors on all scales and redshifts of interest. We show that future large sky coverage KSZ surveys may allow a peculiar velocity power spectrum estimates of an accuracy reaching ∼10 per cent.     

The distribution of sodium ions in aluminosilicate glasses: a high-field Na-23 MAS and 3Q MAS NMR study

The local configurations around sodium ions in silicate glasses and melts and their distributions have strong implications for the dynamic and static properties of melts and thus may play important roles in magmatic processes. The quantification of distributions among charge-balancing cations, including Na⁺ in aluminosilicate glasses and melts, however, remains a difficult problem that is relevant to high-temperature geochemistry as well as glass science.Here, we explore the local environment around Na⁺ in charge-balanced aluminosilicate glasses (the NaAlO₂-SiO₂ join) and its distribution using ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy at varying magnetic fields of 9.4, 14.1, and 18.8 T, as well as triple-quantum (3Q)MAS NMR spectroscopy at 9.4 T, to achieve better understanding of the extent of disorder around this cation. We quantify the extent of this disorder in terms of changes in Na-O distance (d[Na-O]) distributions with composition and present a structural model favoring a somewhat ordered Na distribution, called a “perturbed” Na distribution model. The peak position in ²³Na MAS spectra of aluminosilicate glasses moves toward lower frequencies with increasing Si/Al ratios, implying that the average d(Na-O) increases with increasing R. The peak width is significantly reduced at higher fields (14.1 and 18.8 T) because of the reduced effect of second-order quadrupolar interaction, and ²³Na MAS NMR spectra thus provide relatively directly the Na chemical shift distribution and changes in atomic environment with composition. Chemical shift distributions obtained from ²³Na 3Q MAS spectra are consistent with MAS NMR data, in which deshielding decreases with R. The average distances between Na and the three types of bridging oxygens (BOs) (Na-{Al-O-Al}, Na-{Si-O-Al}, and Na-{Si-O-Si}) were obtained from the correlation between d(Na-O) and isotropic chemical shift. The calculated d(Na-{Al-O-Al}) of 2.52 Å is shorter than the d(Na-{Si-O-Si}) of 2.81 Å, and d(Na-{Al-O-Al}) shows a much narrower distribution than the other types of BOs. ²³Na chemical shifts in binary (Al-free) sodium silicate glasses are more deshielded and have ranges distinct from those of aluminosilicate glasses, implying that d(Na-NBO) (nonbridging oxygen) is shorter than d(Na-BO) and that d(Na-{Si-O-Si}) in binary silicates can be shorter than that in aluminosilicate glasses. The results given here demonstrate that high-field ²³Na NMR is an effective probe of the Na⁺ environment, providing not only average structural information but also chemically and topologically distinct chemical shift ranges (distributions) and their variation with composition and their effects on static and dynamic properties.     

The enthalpy of fusion of anorthite

The high-temperature enthalpies of liquid and glassy CaAl₂Si₂O₈ were measured by drop calorimetry using a diphenyl ether drop calorimeter. These data are combined with published values of the high-temperature enthalpy of crystalline anorthite and the enthalpy of vitrification of anorthite to obtain the enthalpy of fusion of anorthite. Analysis of the data yields the following preferred values (enthalpy in kcal/mol, uncertainty limits correspond to two standard deviations):enthalpy of vitrification at 985 K, _v H _{v 985}=18.6±0.6; enthalpy of the liquid at 1,830 K, H ₁₈₃₀ ^l ₃₀₀ ^g =130.4±1.2; enthalpy of the glass at 985 K, H ₉₈₅ ^g -H ₃₀₀ ^g =46.7±0.4; enthalpy of crystalline anorthite between 985 and 1,830 K, H ₁₈₃₀ ^c -H ₉₈₅ ^c =69.9±1.4; calculated enthalpy of fusion of anorthite at 1,830 K, _f H ₁₈₃₀= 32.4±2.1.The average heat capacity of supercooled liquid CaAl₂Si₂O₈ between the glass transition (T _g 1,086 K) and the melting point (T _f7=1,830 K) is 102 ± 2 cal/mol/K. The large difference between the enthalpy of fusion and the enthalpy of vitrification for the minerals anorthite and diopside is emphasized. The practice of assuming _fH _vH should be discontinued for silicate compounds for which T _f T _g.