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.     

Correlation of foreshocks and aftershocks and asperities

A close correlation in spatial distribution of local seismic activity and energy release patterns before and after the 1979 Petatlan, Mexico earthquake suggests heterogeneity within the fault plane of this major low-angle thrust event associated with subduction along the Middle America Trench. A simple two-asperity model is proposed to account for the complexity. Foreshocks and aftershocks of the neighboring 1981 Playa Azul earthquake showed a similar pattern. As both events occurred at the junction of the Orozco Fracture Zone and the Middle America Trench, we speculate that the observed complex fault plane is caused by subduction of the rugged ocean floor of the Orozco Fracture Zone. Short-term precursory seismicity prior to the Petatlan earthquake can be explained by using the asperity model and migration of a slip front from the south-east to the north-west across the main shock source region.     

Anomalous hydrogen emissions from the San Andreas fault observed at the Cienega Winery,central California

We began continuous monitoring of H₂ concentration in soil along the San Andreas and Calaveras faults in central California in December 1980, using small H₂/O₂ fuel-cell sensors. Ten monitoring stations deployed to date have shown that anomalous H₂ emissions take place occasionally in addition to diurnal changes. Among the ten sites, the Cienega Winery site has produced data that are characterized by very small diurnal changes, a stable baseline, and remarkably distinct spike-like H₂ anomalies since its installation in July 1982. A major peak appeared on 1–10 November 1982, and another on 3 April 1983, and a medium peak on 1 November 1983. The occurrences of these peaks coincided with periods of very low seismicity within a radius of 50 km from the site. In order to methodically assess how these peaks are related to earthquakes, three H₂ degassing models were examined. A plausible correlational pattern was obtained by using a model that (1) adopts a hemicircular spreading pattern of H₂ along an incipient fracture plane from the hypocenter of an earthquake, (2) relies on the FeO–H₂O reaction for H₂ generation, and (3) relates the accumulated amount of H₂ to the mass of serpentinization of underlying ophiolitic rocks; the mass was tentatively assumed to be proportional to the seismic energy of the earthquake.     

Thermal histories of the core and mantle

Recognition that the cooling of the core is accomplished by conduction of heat into a thermal boundary layer (D″) at the base of the mantle, partly decouples calculations of the thermal histories of the core and mantle. Both are controlled by the temperature-dependent rheology of the mantle, but in different ways. Thermal parameters of the Earth are more tightly constrained than hitherto by demanding that they satisfy both core and mantle histories. We require evolution from an early state, in which the temperatures of the top of the core and the base of the mantle were both very close to the mantle solidus, to the present state in which a temperature increment, estimated to be ～ 800 K, has developed across D″. The thermal history is not very dependent upon the assumption of Newtonian or non-Newtonian mantle rheology. The thermal boundary layer at the base of the mantle (i.e., D″) developed within the first few hundred million years and the temperature increment across it is still increasing slowly. In our preferred model the present temperature at the top of the core is 3800 K and the mantle temperature, extrapolated to the core boundary without the thermal boundary layer, is 3000 K. The mantle solidus is 3860 K. These temperatures could be varied within quite wide limits without seriously affecting our conclusions. Core gravitational energy release is found to have been remarkably constant at ～ 3 × 10¹¹ W. nearly 20% of the core heat flux, for the past 3 × 10⁹ y, although the total terrestrial heat flux has decreased by a factor of 2 or 3 in that time. This gravitational energy can power the “chemical” dynamo in spite of a core heat flux that is less than that required by conduction down an adiabatic gradient in the outer core; part of the gravitational energy is used to redistribute the excess heat back into the core, leaving 1.8 × 10¹¹ W to drive the dynamo. At no time was the dynamo thermally driven and the present radioactive heating in the core is negligibly small. The dynamo can persist indefinitely into the future; available power 10¹⁰ y from now is estimated to be 0.3 × 10¹¹ W if linear mantle rheology is assumed or more if mantle rheology is non-linear. The assumption that the gravitational constant decreases with time imposes an implausible rate of decrease in dynamo energy. With conventional thermodynamics it also requires radiogenic heating of the mantle considerably in excess of the likely content of radioactive elements.     

Volatiles H2O,CO2, and Cl in a subduction related basalt

The products of the 1974 eruption of Fuego, a subduction zone volcano in Guatemala, have been investigated through study of silicate melt inclusions in olivine. The melt inclusions sampled liquids in regions where olivine, plagioclase, magnetite, and augite were precipitating. Comparisons of the erupted ash, groundmass, and melt inclusion compositions suggest that the inclusions represent samples of liquids present in a thermal boundary layer of the magma body. The concentrations of H₂O and CO₂ in glass inclusions were determined by a vacuum fusion manometric technique using individual olivine crystals (Fo77 to Fo71) with glass inclusion compositions that ranged from high-alumina basalt to basaltic andesite. Water, Cl, and K₂O concentrations increased by a factor of two as the olivine crystals became more iron-rich (Fo77 to Fo71) and as the glass inclusions increased in SiO₂ from 51 to 54 wt.% SiO₂. The concentration of H₂O in the melt increased from 1.6 wt.% in the least differentiated liquid to about 3.5% in a more differentiated liquid. Carbon dioxide is about an order of magnitude less abundant than H₂O in these inclusions. The gas saturation pressures for pure H₂O in equilibrium with the melt inclusions, which were calculated from the glass inclusion compositions using the solubility model of Burnham (1979), are given approximately by P(H₂O)(Pa)=(SiO₂−48.5 wt.%) × 1.45 × 10⁷. The concentrations of water in the melt and the gas saturation pressures increased from about 1.5% to 3.5% and from 300 to 850 bars, respectively, during pre-eruption crystallization.     

The latitudinal distribution of carbon monoxide across the pacific from California to Antarctica

The results of a research study of the carbon monoxide concentration from California to 90° S, Antarctica are presented. The data both extend and support other research studies of the latitudinal distribution of carbon monoxide in that higher concentrations are evident over the Northern Hemisphere than over the Southern Hemisphere. Carbon monoxide concentrations range between 50 to 60 ppb with a few peaks into the 60s in the latitudinal area south of the ITCZ and values of 80 ppb or higher at latitudes north of Hawaii. A comparison is also made of carbon monoxide and ozone concentrations along the flight tract between California and Antarctica, over the Ellsworth Mountains of Antarctica, and between 78° S and the South Pole. These ozone-carbon monoxide data show statistically significant negative correlations in the upper troposphere and lower stratosphere over Antarctica. It is believed that this is a good indication of mixing across the tropopause.     

Solution of H2O in diopside melts: a thermodynamic model

Structural similarities between dry diopside melt and superhydrous albite melt (X _w >0.5) — both lack three-dimensional silicate units — suggest that thermodynamic relations may be similar. A model based on that assumption successfully predicts diopside melting relations and H₂O solubilities. For the model, the three partial differential equations describing solution of H₂O in albite melt for X _w >0.5 have been integrated for diopside melt from X _w =0 to X _w at least as large as 0.76, with two exceptions: an alternative partial differential equation for Henrian solution of H₂O in dilute melts was applied for X _w <0.20, and an alternative differential equation for the pressure dependence of a _w at pressures below 2 kbar was developed. The latter alternative equation yields relatively small ¯V_w's at low pressures rather than the large ¯V_w's calculated from the equation from the albite system. Available experimental solubility data are not precise enough to offer a choice between the small-¯V_w and large-¯V_w equations. Integration of all the partial differential equations was constrained solely by the P and T of a single experimentally-determined point on the H₂O-saturated solidus.Solubilities calculated by a Henrian-analogue solution model (a _di=X _di ² ) from the experimental H₂O saturated solidus lie outside experimental solubility constraints for dilute melts. On the other hand, a Henrian model (a _di=X_di) successfully predicts solubilities in dilute melts. The formulation of the Henrian model and magnitudes of model molar entropies of solution are consistent with the hypothesis that H₂O dissolves in diopside melt as an essentially undissociated species with little ordering on melt structural sites. That species could in turn be consistently, if not uniquely, interpreted to be molecular H₂O or a hydroxylation (OH^–) complex formed from nonbridging oxygens.     

Determination of Boron in 35 International Geochemical Reference Materials by Thermal Neutron Capture Prompt Gamma-ray Spectrometry

Concentrations of boron in 35 silicate reference materials are measured by thermal neutron capture gamma-ray spectrometry. Results are compared for NBS, USGS, and CCRMP reference materials with values from the literature. The use of two prompt gamma facilities at Los Alamos are discussed.     

Distribution and mode of occurrence of zinc and lead in glacial soils

The distribution and mode of occurrence of zinc and lead have been examined in glacial soils developed over a complex Precambrian marble-paragneiss terrain in the Adirondack Mountains of New York. Based on distribution within the soil profiles, zinc is enriched in the B₁ horizon of soils sampled over marble and lead is generally enriched in the A horizon, particularly in soils developed over paragneiss. Contrast is calculated using

Full-size image (1K)

, where is the mean of n_A anomalous and n_B background samples, and S_p is the pooled standard deviation) for zinc, lead and cold-extractable heavy metals in soils sampled over marble and paragneiss. The t-values indicate that the B₁, soil horizon is the most suitable for sampling on a regular basis, even though lead is most concentrated in the A horizon.The distribution of zinc and lead among exchangeable, organic, iron-manganese oxide, clay, silt and sand fractions of B₁ horizons from two anomalous and one background soil indicates that both zinc and lead are tied up principally in iron and manganese oxides. The anomalous samples exhibit zinc enrichment in the Fe-oxide digestion and high Mn/Fe ratios for the Mn-oxide digestion (as well as the total analysis). In terms of total contribution to the sample, significant proportions of zinc in the clastic fraction can be attributed to zinc substitution into clays plus the ineffective removal of Fe-oxides by the ammonium oxalate extraction procedure. Lead, on the other hand, occurs in significant concentrations in clay, silt and sand as well as Fe- and Mn-oxides, probably as a trace constituent in feldspars or adsorbed onto clay surfaces.     

Temperature dependence of calcite dissolution kinetics between 1 and 62°C at pH 2.7 to 8.4 in aqueous solutions

The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole^?1 for Carrara marble and 46 ± 4 kJ mole^?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole^?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole^?1 and this high EAAE is consistent with transport dependence on product diffusion in this H⁺-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole^?1, also decreasing with increasing temperature. This is compatible with H⁺-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H⁺-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H⁺-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.