The structural state of iron in oxidized vs. reduced glasses at 1 atm: A57Fe Mössbauer study

A general model for the structural state of iron in a variety of silicate and aluminosilicate glass compositions in the systems Na₂O-Al₂O₃-SiO₂-Fe-O, CaO-Al₂O₃-SiO₂-Fe-O, and MgO-Al₂O₃-SiO₂-Fe-O is proposed. Quenched melts with variable Al/Si and NBO/T (average number of nonbridging oxygens per tetrahedrally coordinated cation), synthesized over a range of temperatures and values of oxygen fugacity, are analyzed with⁵⁷Fe Mössbauer spectroscopy. For oxidized glasses with Fe³⁺/∑Fe>0.50, the isomer shift for Fe³⁺ is in the range ～0.22–0.33 mm/s and ～0.36 mm/s at 298 K and 77 K, respectively. These values are indicative of tetrahedrally coordinated Fe^3?. This assignment is in agreement with the interpretation of Raman, luminescence, and X-ray,K-edge absorption spectra. The values of the quadrupole splitting are ～0.90 mm/s (298 K and 77 K) in the Na-aluminosilicate glasses and compare with the values of 1.3 mm/s and 1.5 mm/s for the analogous Ca- and Mg-aluminosilicate compositions. The variations in quadrupole splittings for Fe³⁺ are due to differences in the degree of distortion of the tetrahedrally coordinated site in each of the systems. The values of the isomer shifts for Fe²⁺ ions in glasses irrespective of Fe³⁺/∑Fe are in the range 0.90–1.06 mm/s at 298 K and 1.0–1.15 mm/s at 77 K. The corresponding range of values of the quadrupole splitting is 1.75–2.10 mm/s at 298 K and 2.00–2.35 mm/s at 77 K. The temperature dependence of the hyperfine parameters for Fe²⁺ is indicative of noninteracting ions, but the values of the isomer shift are intermediate between those values normally attributable to tetrahedrally and octahedrally coordinated Fe²⁺. The assignment of the isomer-shift values of Fe²⁺ to octahedral coordination is in agreement with the results of other spectral studies. For reduced glasses (Fe³⁺/∑Fe≈<0.50), the value of the isomer shift for Fe³⁺ at both 298 K and 77 K increases and is linearly correlated with decreasing Fe³⁺/∑Fe in the range of \(f_{O_2 } \) between 10^?3 and 10^?6 atm when a single quadrupole-split doublet is assumed to represent the absorption due to ferric iron. The increase in value of the isomer shift with decreasing \(f_{O_2 } \) is consistent with an increase in the proportion of Fe³⁺ ions that are octahedrally coordinated. The concentration of octahedral Fe³⁺ is dependent on the \(T - f_{O_2 } \) conditions, and in the range of log \(f_{O_2 } \) between 10^?2.0 and 10^?5 a significant proportion of the iron may occur as iron-rich structural units with stoichiometry similar to that of inverse spinels such as Fe₃O₄, in addition to isolated Fe²⁺ and Fe³⁺ ions.     

Petrological evidence for the development of refolded folds during a single deformational event

The Pelona Schist, which forms the lower plate of the Vincent thrust in the San Gabriel Mountains of southern California, has undergone a complex history of folding. The youngest folds in the schist (style 2 folds) range in shape from open to tight and fold both compositional layering and schistosity. These are superposed upon isoclinal folds with axial-plane schistosity (style 1 folds) that, in turn, overprint older isoclinal folds (also called style 1 folds). Samples from the hinges of style 2 folds contain two generations of muscovite. Muscovites of the older generation are parallel to the folded (style 1) schistosity. The newer muscovites recrystallized during and/or after style 2 folding. Microprobe analysis indicates that the two generations of muscovite are very similar in composition, although the new muscovites tend to have slightly higher paragonite and celadonite contents than the old muscovites. From the gross similarity of the two groups of muscovite, it is concluded that the style 1 and style 2 folds were produced during a single progressive deformation. The slightly higher paragonite and celadonite contents of the new muscovites are thought to indicate that both pressure and temperature were increasing during the deformation. This is consistent with the deformation being due to underthrusting of the Pelona Schist beneath the upper plate of the Vincent thrust.     

Boundary-layer structure near the cold front of a marine cyclone during “ERICA”

The boundary layer in the warm sector of a moderately deepening winter cyclone during the Experiment on Rapidly Intensifying Cyclones over the Atlantic (ERICA) is studied near the cold front. Data from the National Center for Atmospheric Research Electra research aircraft are used to examine mean and turbulence quantities. The aircraft data and supplemental data from ships, drifting buoys and moored buoys reveal an equivalent-barotropic pressure field. The area is found to be dominated by gradients in temperature and in turbulent fluxes, with changes occurring over 100 km horizontally being comparable to changes over 350 m vertically. The horizontal components of the gradients are found to be a maximum in a direction perpendicular to the front. Cross-sections perpendicular to the front are used to illustrate boundary-layer structure. Profiles of wind speed, stress, wind direction and stress direction are estimated from an Ekman model that is modified to take into account the equivalent-barotropic pressure field. Comparison of profiles from the model to the aircraft-measured data show reasonable agreement far from the front (100 km) when the model uses a constant eddy viscosity of approximately 6 kg m^–1 s^–1. Near the front there is less agreement with the model. Profiles of turbulent fluxes of momentum, heat and latent heat are divergent, with along-wind momentum flux negative and decreasing upward, cross-wind momentum flux positive and increasing upward, and heat flux and latent heat flux small, positive and decreasing upward. Far from the front, the turbulent kinetic energy budget shows that dissipation balances shear production. However, near-front behavior has an imbalance at low altitude, with shear production appearing as a TKE sink.     

Potential for Solute Retardation on Monitoring Well Sand Packs and Its Effect on Purging Requirements for Ground Water Sampling

Monitoring well sand packs are theoretically capable of retarding metal ions and organic contaminants. If this retardation does indeed occur it may have a significant effect on the purging requirements of newly installed monitoring wells. Calculations based on mass balance and retardation concepts demonstrate that if common guidelines for well purging are followed, contaminants may not be detected or may be detected in lower concentrations than are actually present in the ground water. This problem is greatest in relatively shallow wells installed in low to moderate permeability materials. In most cases, the effect of solute retardation in the sand pack can be avoided simply by additional purging prior to the first sampling of the monitoring well. Common purging guidelines can then be applied to subsequent samplings. The methodology outlined in this paper can be used to calculate the purging requirements of existing monitoring wells or it may be applied to alternative monitoring well designs to test which will require the smallest volume of purged water.     

Lake Søbygaard: a shallow lake in recovery after a reduction in phosphorus loading

The development and recovery of a shallow and hypertrophic lake following a reduction in the external phosphorus load has been documented. In spite of this reduction, phosphorus concentrations and phytoplankton biomass in the lake water are still very high. The reason for this development can be explained by three main factors: (1): the sediment has been accumulating a large phosphorus pool which is now causing a high internal phosphorus load, (2) due to the shallow conditions, resuspension of the upper sediment often takes place because of wind action and thereby increases the phosphorus loading from the sediment, (3) the development of a large population of planktivorous fish decreases the zooplankton biomass resulting in the development of a large phytoplankton biomass.     

Olivine phenocrysts of Hawaiian olivine tholeiite and oceanite

Olivine phenocrysts of Hawaiian tholeiites display a variety of textures and a variation in composition which is due to supercooled crystallization. The highest forsterite content measured is 91%, and the highest magnesia content estimated for a tholeiitic liquid is 17%, using the olivine geothermometer. The liquid of this composition may be either a primary magma or a primitive magma. It is not yet possible to specify any particular composition range for the primary Hawaiian tholeiites.