The nature of hydroxyl groups in aluminosilicate glasses: Quantifying Si-OH and Al-OH abundances along the SiO2-NaAlSiO4 join by H, Al-H and Si-H NMR spectroscopy

The combined results of ²⁷Al-¹H and ¹H-²⁹Si-¹H cross polarization NMR experiments for hydrous glasses (containing 0.5-2 wt% water) along the SiO₂-NaAlSiO₄ join confirm that the dissolution mechanism of water in aluminosilicate glasses is fundamentally the same as for Al-free systems, i.e. the dissolved water ruptures oxygen bridges and creates Si-OH and Al-OH groups, in addition to forming molecular water (H₂O_mol). The fraction of Al-OH increases non-linearly as the Al content increases with up to half of the OH groups as Al-OH for compositions close to NaAlSiO₄. The relative abundances of the different species are controlled by the degree of Al-avoidance and the relative tendency of hydrolysis of the different types of oxygen bridges, Si-O-Si, Si-O-Al and Al-O-Al. A set of homogeneous reactions is derived to model the measured Al-OH/Si-OH speciation, and the obtained equilibrium constants are in agreement with literature data on the degree of Al-avoidance. With these equilibrium constants, the abundance of the different oxygen species, i.e. Si-O-Si, Si-O-Al, Al-O-Al, Si-OH, Al-OH and H₂O_mol, can be predicted for the entire range of water and Al contents.     

LavAtmos: An open-source chemical equilibrium vaporization code for lava worlds

To date, over 500 short-period rocky planets with equilibrium temperatures above 1500 K have been discovered. Such planets are expected to support magma oceans, providing a direct interface between the interior and the atmosphere. This provides a unique opportunity to gain insight into their interior compositions through atmospheric observations. A key process in doing such work is the vapor outgassing from the lava surface. LavAtmos is an open-source code that calculates the equilibrium chemical composition of vapor above a dry melt for a given composition and temperature. Results show that the produced output is in good agreement with the partial pressures obtained from experimental laboratory data as well as with other similar codes from literature. LavAtmos allows for the modeling of vaporization of a wide range of different mantle compositions of hot rocky exoplanets. In combination with atmospheric chemistry codes, this enables the characterization of interior compositions through atmospheric signatures.     

MERIS and the red-edge position

The Medium Resolution Imaging Spectrometer (MERIS) is a payload component of Envisat-1. MERIS will be operated over land with a standard 15 band setting acquiring images with a 300 m spatial resolution. The red-edge position (REP) is a promising variable for deriving foliar chlorophyll concentration, which plays an important role in ecosystem processes. The objectives of this paper are: (1) to study which factors effect the REP of vegetation, (2) to study whether this REP can be derived from the MERIS standard band setting and (3) to show what REP represents at the scale of MERIS data. Two different data sets were explored for simulating the REP using MERIS bands: (1) simulated data using reflectance models and (2) airborne reflectance spectra of an agricultural area obtained by the airborne visible-infrared imaging spectrometer (AVIRIS). A “linear method”, assuming a straight slope of the reflectance spectrum around the midpoint of the slope, was a robust method for determining the REP and the MERIS bands at 665, 708.75, 753.75 and 778.75 nm could be used for applying the “linear method” for REP estimation. Results of the translation to the scale of MERIS data were very promising for applying MERIS at, for instance, the ecosystem level.     

Late Quaternary deglaciation and climate history of the Larsemann Hills (East Antarctica)

The Late Quaternary climate history of the Larsemann Hills has been reconstructed using siliceous microfossils (diatoms, chrysophytes and silicoflagellates) in sediment cores extracted from three isolation lakes. Results show that the western peninsula, Stornes, and offshore islands were ice‐covered between 30 000 yr BP and 13 500 cal. yr BP. From 13 500 cal. yr BP (shortly after the Antarctic Cold Reversal) the coastal lakes of the Larsemann Hills were deglaciated and biogenic sedimentation commenced. Between 13 500 and 11 500 cal. yr BP conditions were warmer and wetter than during the preceding glacial period, but still colder than today. From 11 500 to 9500 cal. yr BP there is evidence for wet and warm conditions, which probably is related to the early Holocene climate optimum, recorded in Antarctic ice cores. Between 9500 and 7400 cal. yr BP dry and cold conditions are inferred from high lake‐water salinities, and low water levels and an extended duration of nearshore sea‐ice. A second climate optimum occurred between 7400 and 5230 cal. yr BP when stratified, open water conditions during spring and summer characterised the marine coast of Prydz Bay. From 5230 until 2750 cal. yr BP sea‐ice duration in Prydz Bay increased, with conditions similar to the present day. A short return to stratified, open water conditions and a reduction in nearshore winter sea‐ice extent is evident between 2750 and 2200 cal. yr BP. Simultaneously, reconstructions of lake water depth and salinity suggests relatively humid and warm conditions on land between 3000 and 2000 cal. yr BP, which corresponds to a Holocene Hypsithermal reported elsewhere in Antarctica. Finally, dry conditions are recorded around 2000, between 760 and 690, and between 280 and 140 cal. yr BP. These data are consistent with ice‐core records from Antarctica and support the hypothesis that lacustrine and marine sediments on land can be used to evaluate the effect of long‐term climate change on the terrestrial environment. Copyright © 2004 John Wiley & Sons, Ltd.     

Structural control on bulk melt properties: Single and double quantum Si NMR spectroscopy on alkali-silicate glasses

The structure of 21 binary potassium, rubidium and cesium silicate glasses (in the range 15-50 mol% alkali oxide) was analyzed by ²⁹Si single quantum and double quantum MAS NMR spectroscopy. Their glass transition temperatures (T_g) were measured by calorimetry. The chemical shifts and the relative abundance of Qⁿ species correlate with the cationic field strength (Z/r) of the network modifier. A correlation is observed between T_g and the inverse of the entropy of mixing of the different Qⁿ species, which is explained in the framework of the Adam-Gibbs relaxation theory. At high alkali content, up to 44% of the SiO₄ tetrahedra are part of three-membered rings. At a given alkali content, the abundance of these rings increases with increasing cation size. The abundance of three-membered rings in K-silicate melts correlates with a temperature and a non-linear composition dependence of the heat capacity. It is also a possible cause for the anomalous volumetric behavior of potassium silicate glasses.     

Compressibility of molten Apollo 17 orange glass and implications for density crossovers in the lunar mantle

We performed density measurements on a synthetic equivalent of lunar Apollo 17 74,220 “orange glass”, containing 9.1 wt% TiO₂, at superliquidus conditions in the pressure range 0.5-8.5 GPa and temperature range 1723-2223 K using the sink/float technique. In the lunar pressure range, two experiments containing pure forsterite (Fo₁₀₀) spheres at 1.0 GPa and 1727 K, and at 1.3 GPa-1739 K, showed neutral buoyancies, indicating that the density of molten orange glass was equal to the density of Fo₁₀₀ at these conditions (3.09 ± 0.02 g cm⁻³). A third tight sink/float bracket using Fo₉₀ spheres corresponds to a melt density of 3.25 ± 0.02 g cm⁻³ at ∼2.8 GPa and ∼1838 K.Our data predict a density crossover for the molten orange glass composition with equilibrium orthopyroxene at ∼2.8 GPa, equivalent to a depth of ∼600 km in the lunar mantle, and a density of ∼3.25 g cm⁻³. This crossover depth is close to the orange glass multiple saturation point, representing its minimum formation depth, at the appropriate oxygen fugacity (2.8-2.9 GPa). A density crossover with equilibrium olivine is predicted to fall outside the lunar pressure range (>4.7 GPa), indicating that molten orange glass is always less dense than its equilibrium olivines in the Moon. Our data therefore suggest that that lunar liquids with orange glass composition are buoyant with respect to their source region at P < ∼2.8 GPa, enabling their initial rise to the surface without the need for additional external driving forces.Fitting the density data to a Birch-Murnaghan equation of state at 2173 K leads to an array of acceptable solutions ranging between 16.1 and 20.3 GPa for the isothermal bulk modulus K₂₁₇₃ and 3.6-8 for its pressure derivative K′, with best-fit values K₂₁₇₃ = 18.8 GPa and K′ = 4.4 when assuming a model 1 bar density value of 2.86 g cm⁻³. When assuming a slightly lower 1 bar density value of 2.84 g cm⁻³ we find a range for K₂₁₇₃ of 14.4-18.0 and K′ 3.7-8.7, with best-fit values of 17.2 GPa and 4.5, respectively.     

Do shorebirds graze down zoobenthic biomass at the Banc d'Arguin tidal flats in Mauritania?

The 500 km² of tidal flats at the Banc d'Arguin, Mauritania, are a wintering site for over 2 million shorebirds, making this one of the areas with the highest density of shorebirds in the world. In earlier studies, it was found that these huge numbers of birds are dependent on a rather low biomass of benthic animals. To explain this paradoxical situation, we hypothesized that the earlier assessments of biomass in late winter and early spring do not reflect a year-round situation. Benthic biomass may be high when the birds arrive in autumn to be subsequently grazed down in the course of winter. To test this hypothesis, we have determined benthic biomass in September 1988. The result has been compared with a biomass value obtained in February–April 1986 with the same methods and at the same stations. These two biomass values do not differ significantly; so our hypothesis has to be rejected. It has to be admitted, however, that our experimental design cannot discern between differences due to the year of sampling and those due to the season.