Phase equilibrium and calorimetric study of the transition of MnTiO3 from the ilmenite to the lithium niobate structure and implications for the stability field of perovskite

The phase boundary between MnTiO₃ I (ilmenite structure) and MnTiO₃ II (lithium niobate structure) has been determined by analysis of quench products from reversal experiments in a cubic anvil apparatus at 1073–1673 K and 43–75 kbar using mixtures of MnTiO₃ I and II as starting materials. Tight brackets of the boundary give P(kbar)=121.2−0.045 T(K). Thermodynamic analysis of this boundary gives ΔH^o=5300±1000 J·mol⁻¹, ΔS^o = 1.98 ±1J·K⁻¹· mol⁻¹. The enthalpy of transformation obtained directly by transposed-temperature-drop calorimetry is 8359 ±2575 J·mol⁻¹. Possible topologies of the phase relations among the ilmenite, lithium niobate, and perovskite polymorphs are constrained using the above data and the observed (reversible with hysteresis) transformation of II to III at 298 K and 20–30 kbar (Ross et al. 1989). The observed II–III transition is likely to lie on a metastable extension of the II–III boundary into the ilmenite field. However the reversed I–II boundary, with its negative dP/ dT does represent stable equilibrium between ilmenite and lithium niobate, as opposed to the lithium niobate being a quench product of perovskite. We suggest a topology in which the perovskite occurs stably at low T and high P with a triple point (I, II, III) at or below 1073 K near 70 kbar. The I–II boundary would have a negative P-T slope while the II–III and I–III boundaries would be positive, implying that entropy decreases in the order lithium niobate, ilmenite, perovskite. The inferred positive slope of the ilmenite-perovskite transition in MnTiO₃ is different from the negative slopes in silicates and germanates. These thermochemical parameters are discussed in terms of crystal structure and lattice vibrations.     

Observations of longitudinal roll vortices during arctic cold air outbreaks over open water

An evolving convective Arctic planetary boundary layer (PBL) containing longitudinal roll vortices (rolls) was observed with aircraft data during the 1983 Marginal Ice Zone Experiment and the 1984 Arctic Cyclone Experiment.The PBL is observed to grow rapidly as the very cold and dry air flows off the ice over the relatively warm water. There is very large sensible heat flux, a result of the large surface-air temperature differences. Coherent structures were identified in these PBL's by use of power, coherence squared and phase spectra of the data. A systematic method of separating the rolls from organized thermal plumes was devised, based on theoretical characteristics for roll circulations and the resulting modified mean wind profile. The rapid mixing by the rolls aids in the establishment of equilibrium and an observed adiabatic modified mean Ekman layer. Rolls that form in a thermally neutral atmosphere over ice have different characteristics than those that appear in the unstable stratification over water. The rolls become increasingly more convective in character with distance from the ice edge. They have aspect ratios (wavelength/PBL height) that decrease with distance from the ice edge in agreement with linear theory. This is in contrast to the cloud street wavelength to inversion height ratio which is observed to increase downwind from the ice edge.     

Dissolved oxygen variations in alpine glacial meltwaters

Recent models of chemical weathering in alpine glacial meltwaters suggest that sulphide oxidation is a major source of solute in the distributed component of the subglacial hydrological system. This reaction requires O₂, and may lower dissolved oxygen levels to below saturation with respect to the atmosphere. This should result in an inverse association between SO₇^2- and dissolved oxygen saturation. However, measurements of O₂ saturation in bulk meltwaters draining the Haut Glacier d'Arolla, Switzerland, show that there is a positive association between SO₄^2- and O₂ saturation. The O₂ content of glacial meltwaters depends on the initial content of snow and icemelt, which may be controlled by the rate of melting, and the kinetic balance between O₂ losses (e.g. sulphide oxidation, microbial respiration) and gains (e.g. diffusion of O₂ into solution).     

Polarized X-ray absorption spectroscopy of metal ions in minerals

We have made use of the nearly complete linear polarization of synchrotron radiation to study the polarization dependence of X-ray absorption near-edge structure (XANES) and extended fine structure (EXAFS) in oriented single crystals of gillespite (BaFe²⁺ Si₄O₁₀; Fe^{2 +} in square-planar coordination, point symmetry C ₄), anatase (TiO₂; Ti⁴⁺ in octahedral coordination, point symmetry D _2d), and epidote (Ca₂(Al, Fe³⁺)₃SiO₄)₃(OH); Fe³⁺ in distorted octahedral coordination, point symmetry (C _s). For gillespite, the Fe K-XANES spectrum varies strongly with E-vector orientation of the incident X-ray beam. When the E-vector lies in the plane of the FeO₄ group (i.e., perpendicular to the c-axis), multiple-scattering features at 7127 and 7131 eV intensify, whereas when the E-vector is perpendicular to the plane of the FeO₄ group (i.e., parallel to the c-axis), a strongly-polarized 1s to 4p bound state transition occurs at 7116 eV and a localized continuum resonance occurs at 7122 eV. The Fe-K-EXAFS spectrum of gillespite is also highly polarization dependent. When the E-vector is perpendicular to c, all four nearest-neighbor oxygens around Fe²⁺ contribute to the EXAFS signal; when E is parallel to c, the EXAFS signal from nearest-neighbors is reduced by at least 86%. The unpolarized Ti K-XANES spectrum of anatase has three relatively strong pre-edge features at 4967.1, 4969.9, and 4972.7 eV which have resisted definitive interpretation in past studies. The lowest energy feature has a strong xy polarization dependence, suggesting a large amount of 4p _x,y character, and it is also very sharp, indicating a well-defined transition energy. Both of these observations are consistent with an excitonic state with a binding energy of 2.8 eV. The two higher energy features, which are characteristic of octahedrally-coordinated Ti⁴⁺, show little polarization dependence and are probably due to 1s to 3d bound-state transitions, with a small degree of np character in the final state wavefunction. Interpretation of the polarization dependence of Fe K-XANES spectra for epidote is not as straightforward due to the lower space group symmetry (P2₁/m) relative to gillespite (P4/ncc) and anatase (I4₁/amd) and the lower point group symmetry (C _s) of the M(3) site which contains most of the Fe³⁺ in the epidote structure. However, the presence of a shoulder at 7121 eV in the E parallel to b spectrum and its absence in the E normal to bc spectrum are consistent with it being a 1s to 4p _z bound-state transition. Strong, weakly x, y polarized features near 7126 eV in both spectra are most likely due to localized continuum transitions. Also, the 1s to 3d pre-edge intensity varies in intensity with E-vector orientation which is consistent with displacement of Fe³⁺ from the center of the M(3) octahedral site. Analysis of EXAFS spectra of epidote in these two polarizations yields bond distances which are within 0.04 Å of previous single-crystal X-ray diffraction analysis. This study demonstrates the utility of polarized X-ray absorption spectroscopy in quantifying the energies and orbital compositions of final state wavefunctions associated with various X-ray induced transitions in transition-metal containing minerals. It also shows that reasonably accurate M-O distances can be obtained for individual bonds oriented in crystallographically non-equivalent directions.     

Pahoehoe and aa in Hawaii: volumetric flow rate controls the lava structure

The historical records of Kilauea and Mauna Loa volcanoes reveal that the rough-surfaced variety of basalt lava called aa forms when lava flows at a high volumetric rate (>5–10 m³/s), and the smooth-surfaced variety called pahoehoe forms at a low volumetric rate (<5–10 m³/s). This relationship is well illustrated by the 1983–1990 and 1969–1974 eruptions of Kilauea and the recent eruptions of Mauna Loa. It is also illustrated by the eruptions that produced the remarkable paired flows of Mauna Loa, in which aa formed during an initial short period of high discharge rate (associated with high fountaining) and was followed by the eruption of pahoehoe over a sustained period at a low discharge rate (with little or no fountaining). The finest examples of paired lava flows are those of 1859 and 1880–1881. We attribute aa formation to rapid and concentrated flow in open channels. There, rapid heat loss causes an increase in viscosity to a threshold value (that varies depending on the actual flow velocity) at which, when surface crust is torn by differential flow, the underlying lava is unable to move sufficiently fast to heal the tear. We attribute pahoehoe formation to the flowage of lava at a low volumetric rate, commonly in tubes that minimize heat loss. Flow units of pahoehoe are small (usually <1 m thick), move slowly, develop a chilled skin, and become virtually static before the viscosity has risen, to the threshold value. We infer that the high-discharge-rate eruptions that generate aa flows result from the rapid emptying of major or subsidiary magma chambers. Rapid near-surface vesiculation of gas-rich magma leads to eruptions with high discharge rates, high lava fountains, and fast-moving channelized flows. We also infer that long periods of sustained flow at a low discharge rate, which favor pahoehoe, result from the development of a free and unimpeded pathway from the deep plumbing system of the volcano and the separation of gases from the magma before eruption. Achievement of this condition requires one or more episodes of rapid magma excursion through the rift zone to establish a stable magma pathway.     

Finite element analysis of excavation

The finite element method has often been used to simulate excavation. When the soil is linearly elastic, the results of excavation should be independent of the number of stages in the excavation process, and lack of such independence indicates an incorrect procedure. The simple direct method described in this paper provides the required independence in the case of linearly elastic materials, and hence can be used for multi-stage excavation in non-linear problems without excessive errors. However methods whose errors increase with the number of stages of excavation are quite unsuitable for non-linear problems. Alternative methods of analysis, errors arising from the inability of the elements to model adequately the stress gradients near the toe of the excavation and excavation adjacent to a diaphragm wall are discussed.     

14C content of ten meteorites measured by tandem accelerator mass spectrometry

¹⁴C has been measured in three North American and seven Antarctic meteorites with the Chalk River MP tandem accelerator. In most cases cosmogenic¹⁴C, which is tightly bound, was separated from absorbed atmospheric radiocarbon by stepwise heating extractions. Terrestrial ages obtained by comparing cosmogenic¹⁴C in the meteorite to that in Bruderheim are (7.2 ± 0.6) × 10³ years for Yamato 7304, (11.6 ± 0.4) × 10³ years for Estacado, and range from (32.7 ± 0.5) × 10³ to (41.0 ± 0.8) × 10³ years for six meteorites recovered at Allan Hills and its vicinity. The present upper limit to age determination by the accelerator method varies from 50 × 10³ to 70 × 10³ years depending upon mass and carbon content of the sample. The natural limit caused by cosmic ray production of¹⁴C in silicate rocks at 2000 m elevation is estimated to be (55 ± 5) × 10³ years. “Weathering ages” were estimated for the Antarctic meteorites from the specific activity of loosely-bound CO₂ considered to be absorbed from the terrestrial atmosphere on weathering. The accelerator measurements are in accordance with previous low-level counting measurements but have higher precision and sensitivity.     

Structure and viscosity of rhyolitic composition melts

The average local structure of a rhyolitic composition glass has been determined at 25°C using X-ray radial distribution analysis (RDA) and quasi-crystalline modelling and is best described as similar to that in a stuffed framework composed principally of six-membered rings of Si and Al tetrahedra (basically a stuffed tridymite-like model). Using this model it is possible to calculate a density (2.41 g/cm³) which compares well with the measured density (2.40 g/cm³); a structural model based on four-membered rings (an albite-like model) results in a substantially higher calculated density (2.60 g/cm³). We suggest that the rhyolite glass structural model is appropriate for rhyolitic melts, based on evidence from the recent literature. New viscosity data for an anhydrous rhyolite composition measured between 1200°C and 1500°C are presented and interpreted in terms of our proposed structural model and previous melt structure models for the major normative components of rhyolite. A mechanism for diffusion and viscous flow in framework silicate melts (including rhyolite composition) is proposed on the basis of recent molecular orbital calculations and molecular dynamics simulations of silicate and fluoride melts.