Phase relations and equation-of-state of aluminous Mg-silicate perovskite and implications for Earth's lower mantle

We have investigated the effect of Al³⁺ on the room-temperature compressibility of perovskite for stoichiometric compositions along the MgSiO₃-AlO_1.5 join with up to 25 mol% AlO_1.5. Aluminous Mg-perovskite was synthesized from glass starting materials, and was observed to remain a stable phase in the range of ∼30-100 GPa at temperatures of ∼2000 to 2600 K. Lattice parameters for orthorhombic (Pbnm) perovskite were determined using in situ X-ray diffraction at SPring8, Japan. Addition of Al³⁺ into the perovskite structure increases orthorhombic distortion and unit cell volume at ambient conditions (V₀). Compression causes anisotropic decreases in axial length, with the a axis more compressive than the b and c axes by about 25% and 3%, respectively. The magnitude of orthorhombic distortion increases with pressure, but aluminous perovskite remains stable to pressures of at least 100 GPa. Our results show that substitution of Al³⁺ causes a mild increase in compressibility, with the bulk modulus (K₀) decreasing at a rate of −67±35 GPa/X_Al. This decrease in K₀ is consistent with recent theoretical calculations if essentially all Al³⁺ substitutes equally into the six- and eight-fold sites by charge-coupled substitution with Mg²⁺ and Si⁴⁺. In contrast, the large increase in compressibility reported in some studies with addition of even minor amounts of Al is consistent with substitution of Al³⁺ into six-fold sites via an oxygen-vacancy forming substitution reaction. Schematic phase relations within the ternary MgSiO₃-AlO_1.5-SiO₂ indicate that a stability field of ternary defect Mg-perovskite should be stable at uppermost lower mantle conditions. Extension of phase relations into the quaternary MgSiO₃-AlO_1.5-FeO_1.5-SiO₂ based on recent experimental results indicates the existence of a complex polyhedral volume of Mg-perovskite solid solutions comprised of a mixture of charge-coupled and oxygen-vacancy Al³⁺ and Fe³⁺ substitutions. Primitive mantle with about 5 mol% AlO_1.5 and an Fe³⁺/(Fe³⁺+Fe²⁺) ratio of ∼0.5 is expected to be comprised of ferropericlase coexisiting with Mg-perovskite that has a considerable component of Al³⁺ and Fe³⁺ defect substitutions at conditions of the uppermost lower mantle. Increased pressure may favor charge-coupled substitution reactions over vacancy forming reactions, such that a region could exist in the lower mantle with a gradient in substitution mechanisms. In this case, we expect the physical and transport properties of Mg-perovskite to change with depth, with a softer, probably more hydrated, defect dominated Mg-perovskite at the top of the lower mantle, grading into a stiffer, dehydrated, charge-coupled substitution dominated Mg-perovskite at greater depth.     

Chromite in the Paricutin lava flows (1943–1952)

Small euhedral chromite crystals are found in olivine macrophenocrysts (Fo_80–84) from the basaltic andesites (150 ppm Cr) erupted in 1943–1947, and in orthopyroxene macrophenocrysts of the andesites (75 ppm Cr) erupted in 1947–1952. The majority of the chromite octahedra are 5–20 μm in diameter, and some are found in clusters and linear chains of three or more oriented chromite crystals. The composition of the majority of the chromite grains within olivine and orthopyroxene macrophenocrysts is Fe²⁺/(Fe²⁺+Mg)=0.5–0.6, Cr/(Cr+Al)=0.5–0.6 and Fe³⁺/(Fe³⁺+Al+Cr)=0.2–0.3. The chromite crystals in contact with the groundmass are larger, subhedral, and grade in composition from chromite cores to magnetite rims. Comparison of the composition of chromite with those of other volcanic rocks shows that the most primitive Paricutin chromite is richer in total iron and higher in Fe³⁺/(Fe³⁺+Al+Cr) than primary chromite in most lavas. The linear chains of oriented chromite octahedra are found in olivine and orthopyroxene macrophenocrysts, and in the groundmass. These chromite chains are thought to result from diffusion-controlled crystallization because of the very high partition coefficient (1000) of Cr between chromite and melt. We conclude that chromite was a primary phase in the lavas at the time of extrusion and that magnetite only crystallized after extrusion during cooling of the lava flows. The presence of chromite microphenocrysts in andesitic lavas containing as little as 70 ppm Cr can be explained by dissolved H₂O in the melt depressing the liquidus temperature for orthopyroxene such that chromite becomes a liquidus phase. The influence of dissolved H₂O can also explain the lack of plagioclase macrophenocrysts in most of the lavas and the relatively high partition coefficient (20) of Ni between olivine and melt and the high partition coefficient (40) of Cr between orthopyroxene and melt. The liquidus temperature of the basaltic andesite is estimated to have been less than 1140°C, assuming H₂O>1 wt.%, and the log f_O2 to have been above that of the QFM buffer. The chromite and orthopyroxene liquidus temperature of the andesites, assuming H₂O>1 wt.%, is estimated to have been 1100°C or less. The derivation of the later andesites from the earlier basaltic andesites has been explained by a combination of fractional crystallization of olivine, orthopyroxene and plagioclase, and assimilation of xenoliths. The significantly lower Cr, Ni and Mg of the andesites may have been in part due to the separation of olivine macrophenocrysts plus enclosed chromite crystals from the earlier basaltic andesites.     

Morphology and composition of spinel in Pu’u ’O’o lava (1996–1998), Kilauea volcano, Hawaii

The morphology and composition of spinel in rapidly quenched Pu’u ’O’o vent and lava tube samples are described. These samples contain glass, olivine phenocrysts (3–5 vol.%) and microphenocrysts of spinel (0.05 vol.%). The spinel surrounded by glass occurs as idiomorphic octahedra 5–50 μm in diameter and as chains of octahedra that are oriented with respect to each other. Spinel enclosed by olivine phenocrysts is sometimes rounded and does not generally form chains. The temperature before quenching was calculated from the MgO content of the glass and ranges from 1150°C to 1180°C. The oxygen fugacity before quenching was calculated by two independent methods and the log f_O2 ranged from −9.2 to −9.9 (delta QFM=−1). The spinel in the Pu’u ’O’o samples has a narrow range in composition with Cr/(Cr+Al)=0.61 to 0.73 and Fe²⁺/(Fe²⁺+Mg)=0.46 to 0.56. The lower the calculated temperature for the samples, the higher the average Fe²⁺/(Fe²⁺+Mg), Fe³⁺ and Ti in the spinel. Most zoned spinel crystals decrease in Cr/(Cr+Al) from core to rim and, in the chains, the Cr/(Cr+Al) is greater in the core of larger crystals than in the core of smaller crystals. The occurrence of chains and hopper crystals and the presence of Cr/(Cr+Al) zoning from core to rim of the spinel suggest diffusion-controlled growth of the crystals. Some of the spinel crystals may have grown rapidly under the turbulent conditions of the summit reservoir and in the flowing lava, and the crystals may have remained in suspension for a considerable period. The rapid growth may have caused very local (μm) gradients of Cr in the melt ahead of the spinel crystal faces. The crystals seem to have retained the Cr/(Cr+Al) ratio that developed during the original growth of the crystal, but the Fe²⁺/(Fe²⁺+Mg) ratio may have equilibrated fairly rapidly with the changing melt composition due to olivine crystallization. Six of the samples were collected on the same day at various locations along a 10-km lava tube and the calculated pre-collection temperatures of the samples show a 5°C drop with distance from the vent. The average Fe²⁺/(Fe²⁺+Mg) of the spinel in these samples shows a weak positive correlation with decreasing MgO in the glass of these samples. The range in Cr₂O₃ (0.041–0.045 wt.%) of the glass for these six samples is too small to distinguish a consistent change along the lava tube. The spinel in the Pu’u ’O’o samples shows a zoning trend in a Cr–Al–Fe³⁺ diagram almost directly away from the Cr apex. This compares with a zoning trend in rapidly quenched MORB samples away from Cr coupled with decreasing Fe³⁺. The trend away from Cr displayed by spinel in rapidly quenched samples is in marked contrast to the trend of increasing Fe³⁺ shown by spinel in slowly cooled lava.     

Thermal equation of state of magnesite to 32 GPa and 2073 K

Pressure–volume–temperature relations have been measured to 32 GPa and 2073 K for natural magnesite (Mg_0.975Fe_0.015Mn_0.006Ca_0.004CO₃) using synchrotron X-ray diffraction with a multianvil apparatus at the SPring-8 facility. A least-squares fit of the room-temperature compression data to a third-order Birch–Murnaghan equation of state (EOS) yielded K₀ = 97.1 ± 0.5 GPa and K′ = 5.44 ± 0.07, with fixed V₀ = 279.55 ± 0.02 Å³. Further analysis of the high-temperature compression data yielded the temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.013 ± 0.001 GPa/K and zero-pressure thermal expansion α = a₀ + a₁T with a₀ = 4.03 (7) × 10⁻⁵ K⁻¹ and a₁ = 0.49 (10) × 10⁻⁸ K⁻². The Anderson–Grüneisen parameter is estimated to be δ_T = 3.3. The analysis of axial compressibility and thermal expansivity indicates that the c-axis is over three times more compressible (K_Tc = 47 ± 1 GPa) than the a-axis (K_Tc = 157 ± 1 GPa), whereas the thermal expansion of the c-axis (a₀ = 6.8 (2) × 10⁻⁵ K⁻¹ and a₁ = 2.2 (4) × 10⁻⁸ K⁻²) is greater than that of the a-axis (a₀ = 2.7 (4) × 10⁻⁵ K⁻¹ and a₁ = −0.2 (2) × 10⁻⁸ K⁻²). The present thermal EOS enables us to accurately calculate the density of magnesite to the deep mantle conditions. Decarbonation of a subducting oceanic crust containing 2 wt.% magnesite would result in a 0.6% density reduction at 30 GPa and 1273 K. Using the new EOS parameters we performed thermodynamic calculations for magnesite decarbonation reactions at pressures to 20 GPa. We also estimated stability of magnesite-bearing assemblages in the lower mantle.     

Wildfire effects on extractable elements in ash from a Pinus pinaster forest in Portugal

The aim of this work is to study the effects of a wildfire on water‐extractable elements in ash from a Pinus pinaster forest located in Portugal. The pH, electrical conductivity (EC), calcium (Ca²⁺), magnesium (Mg²⁺), sodium (Na⁺), potassium (K⁺), sodium and potassium adsorption ratio (SPAR), aluminium (Al³⁺), manganese (Mn²⁺), iron (Fe²⁺), zinc (Zn²⁺), sulphur (S), silica (Si) and phosphorous (P) were analysed in ash sampled from a sloped area burned in a wildfire and from litter from a contiguous unburned area, with similar morphological conditions. The results showed that ash leachates had higher pH and EC, and were significantly richer in water‐extractable Ca²⁺, Mg²⁺, Na⁺, K⁺, SPAR, S and Si and significantly poorer in water‐extractable Al³⁺, Fe²⁺, Mn²⁺ and Zn²⁺ than litter solutions. No significant differences were observed in water‐extractable P. The fire changed the ash solute chemistry compared with the unburned litter and increased the sample variability of nutrient distribution with potential implications for plant recovery. Copyright © 2013 John Wiley & Sons, Ltd.     

Fe-Mg interdiffusion in magnesiowüstite up to 35 GPa

Fe-Mg interdiffusivities in (Fe,Mg)O magnesiowüstite have been measured in experiments conducted at pressures of 7-35 GPa and temperatures of 1573-1973 K using a Kawai-type high-pressure apparatus. The diffusion profiles were measured across the interface between MgO and (Fe_0.5,Mg_0.5)O samples by electron microprobe analysis, and the Fe-Mg interdiffusivities were determined as D_Fe-Mg=D₀exp{−E*(1+PV*_Mg/E*_Mg)/RT}, where D₀=4.1(^+16.1_−3.3)×10⁻⁷ m²/s, E*=(1−C_Mg)E*_Fe+C_MgE*_Mg (activation energy for the concentration of Mg, where E*_Fe=113(±74) kJ/mol and E*_Mg=226(±32) kJ/mol), the activation volume V*_Mg=1.8(±1.2)×10⁻⁶ m³/mol. By extrapolating these results to the P-T conditions of the core-mantle boundary, we conclude that the interdiffusivity of Fe-Mg in magnesiowüstite at the bottom of the lower mantle is at least one order of magnitude larger than that at the top of the lower mantle.     

Elasticity of single crystal pyrope and implications for garnet solid solution series

The elastic moduli of a synthetic single crystal of pyrope (Mg₃Al₂Si₃O₁₂) have been determined using a technique based on Brillouin scattering. These results are used in an evaluation of the effect of composition on the elastic properties of silicate garnet solid solution series (Mg, Fe, Mn, Ca)₃ (Al, Fe, Cr)₂ Si₃O₁₂. In the pyralspites (Mg FeMn aluminum garnets), for which a large amount of data is available, this analysis indicates that the bulk modulus K is independent of the Fe²⁺/Mg²⁺ ratio, which is similar to the behavior observed in olivines and pyroxenes. However, the shear modulus μ of the garnets increases by 10% from the Mg to the Fe end member, in contrast to the decrease of μ with Fe content which is observed in olivines and pyroxenes. This contrasting behavior is most probably related to the oxygen coordination of the cation site occupied by Mg²⁺ and Fe²⁺ in these different minerals.     

The solubility mechanisms of volatiles in silicate melts and their relations to crystal-andesite liquid equilibria

The anionic structure of magmatic liquids has been estimated at 1 atm and at pressures corresponding to those of the upper mantle. These estimates are based predominantly on spectroscopic data on binary metal oxide-silica and ternary metal oxide-silica-alumina melts. Structural information on melt compositions in aluminate-silica joins has been used to provide detailed information on the role of Al³⁺ in natural magma at atmospheric and high pressure.Regardless of pressure, andesitic melts may be described as combinations of chain, sheet, and three-dimensional network units. Nearly all Al³⁺ in the magmatic liquid resides in the three-dimensional network units. This Al³⁺ is locally charge-balanced with Na⁺, K⁺, Ca²⁺, and Mg²⁺. In the latter two cases, Al³⁺ and Si⁴⁺ are ordered, whereas for Na⁺ and K⁺, Si⁴⁺ and Al³⁺ are randomly mixed. Solution of water in natural magma results in the formation of new nonbridging oxygens in addition to OH groups attached to Si⁴⁺ and metal cations.On the basis of determined solution mechanisms of CO₂ and H₂O in silicate melts, thermodynamic properties of HO+CO₂, fluids and hydrous silicate melts and melting phase relations in peridotite-H₂O-CO₂, systems, it is found that natural andesitic magma in equilibrium with spinel Iherzolite in the upper mantle (10–20 kbar) must contain at least 5–7 wt.% H₂O. Andesitic magma with 5–7 wt.% H₂O in solution may be described as a mixture of Al-free three-dimensional units, sheets, and chains with a small proportion (less than 10%) of monomers.     

Water and nutrient fluxes in a cool temperate rainforest at the Cordillera de la Costa in southern Chile

Water and nutrient fluxes were studied during a 12-month period in an alerce (Fitzroya cupressoides) forest, located in a remote site at the Cordillera de la Costa (40°05′S) in southern Chile. Measurements of precipitation, throughfall, stemflow, effective precipitation, soil infiltration and stream flow were carried out in an experimental, small watershed. Simultaneously, monthly water samples were collected to determine the concentrations and transport of organic-N, NO₃-N, total-P, K⁺, Ca²⁺, Na⁺ and Mg²⁺ in all levels of forest. Concentration of organic-N, NO₃-N, total-P and K⁺ showed a clear pattern of enrichment in the throughfall, stemflow, effective precipitation and soil infiltration. For Ca²⁺ and Mg²⁺, enrichment was observed in the effective precipitation, soil infiltration and stream flow. Annual transport of K⁺, Na⁺, Ca²⁺ and Mg²⁺ showed that the amounts exported from the forest via stream flow (K⁺=0·95, Na⁺=32·44, Ca²⁺=8·76 and Mg²⁺=7·16 kg ha⁻¹ yr⁻¹) are less than the inputs via precipitation (K⁺=6·39, Na⁺=40·99, Ca²⁺=15·13 and Mg²⁺=7·61 kg ha⁻¹ yr⁻¹). The amounts of organic-N and NO₃-N exported via stream flow (organic-N=1·04 and No₃-N=3·06 kg ha⁻¹ yr⁻¹) were relatively small; however, they represented greater amounts than the inputs via precipitation (organic-N=0·74 and NO₃-N=0·97 kg ha⁻¹ yr⁻¹), because of the great contribution of this element in the superficial soil horizon, where the processes of decomposition of organic material, mineralization and immobilization of the nutrients occurs. © 1998 John Wiley & Sons, Ltd.     

Chemical variations in assemblages including epidote and/or chlorite in the fossil hydrothermal system of Saint Martin (Lesser Antilles)

Epidote and/or chlorite are common minerals in the roots of the fossil geothermal system of Saint Martin (Lesser Antilles). They appear in four distinct assemblages: (1) epidote+actinolite+quartz±magnetite near the contact between the tuffaceous host rocks (andesitic modal composition) and the quartz-diorite intrusion of Philipsburg; (2) epidote+chlorite+quartz in host rocks as far as a lateral distance of about 3 km from the intrusion; (3) epidote+chlorite+haematite+quartz locally in iron and manganese rich host rocks; (4) chlorite±phengite±magnetite appearing as late sealing of porosity in fracture-controlled quartz veins with strongly phengitized wall rocks. All these assemblages constitute a large alteration grading from propylitic alteration to thermal metamorphism (actinolite-bearing assemblage).Detailed microprobe studies of epidotes replacing plagioclases and of chlorites replacing glass and mafic minerals reveal notable compositional variations which have been studied with respect to temperature paleogradients (estimated from fluid inclusions study), distance from the thermal source and f_o2 conditions. The mean Ps+Pm [100 × (Fe³⁺ + Mn³⁺)/(Al³⁺ + Fe³⁺ + Mn³⁺)] of epidotes vary from 21 in the presence of magnetite near the intrusion to 32 in haematite-bearing iron and/or manganese volcanic and sedimentary formations. The intra-grain chemical scattering of epidotes increases with increasing distance of the pluton and decreasing temperature of crystallization. All the chlorites coexisting with epidote are Mg-rich (X_Fe<0.50). Their main compositional variation consists in a significant enrichment in magnesium (toward the chlinochlore end member) in presence of haematite. The intra-grain chemical scattering of chlorite (expressed by the aluminium content in the structural formula) increases with increasing distance of the pluton and decreasing temperature of crystallization. Chlorites associated with phengite and magnetite in vein alteration are Fe- and Al-rich. The Mössbauer spectra indicate that the Fe³⁺ content of chlorite varies between 25 and 32% of total Fe in the presence of epidote; the higher content being attained in the presence of haematite. The Fe³⁺ content of chlorite associated with magnetite and phengite is 16% of total Fe. The compositional variations of epidote and/or chlorite of the four distinct assemblages observed at Saint Martin result from the combined effects of f_O2, temperature, and time of heating. The effect of f_O2 is particularly perceptible in the control of the epidote Ps content, of the chlorite X_Fe ratio of Fe³⁺ distribution between coexisting epidotes and chlorites. Despite the fact that it may be partially canceled out by the effect of f_O2, the variation of compositional ranges of both epidotes and chlorites, which increases toward the outer part of the geothermal system in response to the combination of decreasing temperatures and decreasing time of heating of the rocks, suggests that chemical equilibrium has not been attained in the assemblages bearing epidotes and chlorites.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

Computer-simulation models of scoria cone degradation

Long-term erosional modifications of the relatively simple morphology of scoria (‘cinder') cones are ideally suited for study by field and computer-simulation methods. A series of temporally-distinct cones in the San Francisco and Springerville volcanic fields of Arizona provides the foundation for documenting the degradational evolution of scoria cones in a semi-arid climate. Progressive changes due to erosion are illustrated by the systematic decrease with increasing age of various morphometric parameters, including scoria cone height, cone height/width ratio (H_co/W_co), crater depth/width ratio, and slope angle. For example, Holocene–latest Pleistocene cones in the San Francisco field have a mean H_co/W_co value of 0.178±0.041, a mean maximum slope angle of 29.7±4.2°, and a mean average slope angle of 26.4±7.3°, whereas the group of Pliocene cones have values of 0.077±0.024, 20.5±5.8°, and 8.7±2.7°, respectively. Comparative morphology of scoria cones is a potentially useful dating tool for mapping volcanic fields.In order to better understand the degradational modifications of these volcanic landforms, we have developed a numerical approach to simulate the surficial processes responsible for the erosion of a typical scoria cone. The simulation algorithm can apply either a linear diffusion-equation model or a model with a nonlinear transport law. Using a finite-difference formulation, the simulation operates upon a three-dimensional scoria cone input as a matrix of elevation values. Utilizing both field and model results, the correlation between changing H_co/W_co value, cone age, and computer time step was expressed graphically to derive comprehensive values of the transport or diffusion coefficient (D_f) for both volcanic fields. For the San Francisco volcanic field, D_f had a calculated value of 21.4 m²/kyr for the linear model and 5.3 m/kyr for the nonlinear model, while for the Springerville volcanic field D_f had a calculated value of 24.4 m²/kyr for the linear model and 6.3 m/kyr for the nonlinear model.     

Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

High-resolution garnet chronometry and the rates of metamorphic processes

Garnets in an amphibolite-facies metasediment from Sulitjelma, North Norway yield precise and concordant SmNd, UPb and RbSr ages that relate directly to the pressure (P) and temperature (T) conditions of mineral growth. Differential mineral reaction between graphitic and non-graphitic layers within this sample preserves a record of theP-T and time (t) history experienced during Barrovian regional metamorphism. Garnets in graphitic layers grew during prograde metamorphism at462 ± 16°C and5.2 ± 0.5 kbar under conditions of lowaH₂O, and yield indistinguishable¹⁴⁷Sm¹⁴³Nd and²³⁸U²⁰⁶Pb ages of434.1 ± 1.2 Ma and433.9 ± 1.0 Ma, respectively. In contrast, garnet growth in adjacent graphite-free layers did not occur untilP-T conditions of540 ± 18°C and8.0 ± 1.0 kbar were attained, with continued growth in response to minor heating and decompression with final matrix equilibration at544 ± 16°C and7.0 ± 1.0 kbar. The inclusion-free garnet rims in this assemblage record indistinguishable¹⁴⁷Sm¹⁴³Nd and²³⁸U²⁰⁶Pb ages of424.6 ± 1.2 Ma and423.4± 1.7 Ma, respectively. These results provide precise estimates for average heating and burial rates during prograde metamorphism of 8.6_−4.4^+7.5°C Ma⁻¹ and 0.8_−0.5^+0.9 km Ma⁻¹, respectively. Rb and Sr exchange between coexisting silicates in the graphite-free assemblage continued for some 37 Ma after the “peak” of metamorphism, and require an average cooling rate of about 4.0°C Ma⁻¹ during uplift. These results illustrate a clear relationship between reaction history and the timing of mineral growth and provide definitive constraints on the rates of thermal and tectonic processes accompanying regional metamorphism.     

An experimental investigation of vertical vibration of model footings on sand

Many free and forced vertical vibrations tests were conducted on surface and embedded models for footings on dry and moist poorly graded sand that has the following properties: D₁₀ = 0·21 mm, D₃₀ = 0·305 mm, D₆₀ = 0·423 mm, C_u = 2, C_c = 1·05, G_s = 2·66, γ_max = 1·74 cm⁻³ and γ_min = 1·4 g cm⁻³. The tests were conducted at relative density Dr = 82%. The effect of mass, area, geometry, embedment, saturation, load amplitude and frequency were studied. For this purpose square, rectangular and circular models of concrete footings were chosen. Swieleh sand was chosen as the foundation soil. Results have been obtained for models having different mass, same base shape and area; models of different base area and equal base shape and mass; and models of different base shape geometry and about equal masses and base areas.Forced vertical vibration tests results showed an increase in natural frequency and a reduction in amplitude with the increase in embedment depth, degree of saturation and footing base area. Increasing the mass of model footing resulted in a decrease in the natural frequency while the dynamic response increased. Also, results showed that the circular model footing gives low values of dynamic response in comparison to other models.Free vertical vibration test results showed an increase in damping ratio with increase in the base area of the model footing, depth of embedment and saturation of sand. On the other hand, the results showed a decrease in damping ratio with increase in the footing mass. Circular footing gives the highest value of damping ratio among other footings.Results showed that the best method for evaluating the dynamic stiffness for vertical vibration is using Dobry and Gazetas¹ (J. Geotech. Engng, ASCE, 1986, 112, 109–133) equations together with the formula proposed by Ronald and Bojan² (J. Geotech. Engng, ASCE, 1995, 121, 274–286) for evaluating the equivalent shear modulus.     

Microstructure characteristics of illite from Chuanlingou Formation of Changcheng System in Jixian County,Tianjin City

The microstructure charateristics of illite from the Chuanlinggou Formation of Changcheng System (Chch) in Jixian County, Tianjin City has been studied by means of high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), X-ray energy dispersive spectrum (EDS) and X-ray powder diffraction (XRD). The Kübler index of "illite crystallinity" is 0.505°△2θ, which indicates that the host rock is in a middle diagenetic stage. The chemical analyses of EDS for illite studied indicate a heavily absent in interlayer cation and an average chemical formula of K0.57(Al1.80Mg0.42Fe2 0.12)∑=2.34 (Si2.92Al1.08)∑=4O10(OH)2. It is found, from one-dimensional lattice images, that the layers of illite not only stack in a flat way but also in a curving way. A "matting fabric" illite structure results from stacking faults. Combined with SAED analysis the illite studied can be affirmed as 1M illite. The two-dimensional lattice images are obtained from [100] and [110] incidences, whose lattice images have the same d-values but different intersecting angles. The two-dimensional lattice image with [100] incidence is orthogonal to each other, whilst that with [110] incidence is oblique. This paper provides some important structure information of authigenic clay minerals for the well-known mesoproterozoic section of Jixian County.     

Thermal equation of state of magnesiowüstite (Mg0.6Fe0.4)O

Volume measurements for magnesiowüstite (Mg_0.6Fe_0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂K_T/∂P)_T fixed at 4, we obtained K₀=158(2) GPa, (∂K_T/∂T)_P=−0.029(3) GPa K⁻¹, (∂K_T/∂T)_V=−3.9(±2.3)×10⁻³ GPa K⁻¹, and α_T=3.45(18)×10⁻⁵+1.14(28)×10⁻⁸T. The K₀, (∂K_T/∂T)_P, and (∂K_T/∂T)_V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg_0.6Fe_0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg_1−xFe_x)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO₃ perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg_0.6Fe_0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.     

Bolide impacts, acid rain, and biospheric traumas at the Cretaceous-Tertiary boundary

Large projectiles impacting the Earth will cause severe shock heating and chemical reprocessing of the Earth's atmosphere. This occurs during atmospheric entry and, more importantly, as a result of the supersonic plume ejected on impact. In particular, very large amounts of nitric oxide would result from the impact of the putative Cretaceous-Tertiary bolide(s). We present models of the shock chemistry, the conversion of NO to NO₂ and thence to nitrous and nitric acids, and the global dispersion of the NO₂ and acids. Two plausible projectiles are considered: an ice-rich long-period comet and a much smaller rock-metal asteroid. The comet produces semi-global atmospheric NO₂ mixing ratios of 0.1% while the asteroid produces these high mixing ratios only in the immediate region of the impact. The comet produces concentrated nitrous and nitric acid rain with apH ≈ 0–1.5 globally. The asteroid produces rain with apH ≈ 0–1 near the impact and≈ 4–5 globally. Immediate environmental effects of these nitrogen species include inhibition of photosynthesis due to extinction of solar radiation by NO₂, foliage damage due to exposure to NO₂ and HNO₃, toxicosis resulting from massive mobilization of soil trace metals, and respiratory damage due to exposure to NO₂. The acid rain decreases the pH of the oceanic mixed layer affecting the stability of calcite with important implications for the survival of calcareous-shelled organisms and for exhalation of CO₂ from the mixed layer to the atmosphere. Longer-term environmental effects perhaps≈ 1000years in duration include a global warming due to the sudden CO₂ injection and the simultaneous extinction of the ocean micro-organisms which normally help remove CO₂ from the atmosphere-mixed layer system. Havens for survival include carbonate-buffered lakes and burrows. This acid rain theory therefore serves to explain the peculiar selectivity of the extinctions seen at the Cretaceous-Tertiary boundary. The first few years of acid rain will lead to massive weathering rates of continental soils characterized by large ratios of the relatively insoluble metals (e.g. Be²⁺, Al³⁺, Hg²⁺, Cu⁺, Fe²⁺, Fe³⁺, Tl³⁺, Pb²⁺, Cd²⁺, Mn²⁺, Sr²⁺) to the more soluble metals (Ca²⁺, Mg²⁺) which should have left a clear signal in the fossils of neritic organisms and in unperturbed neritic sediments near river deltas if such sediments still exist for the Cretaceous-Tertiary time frame.     

Hydrogeochemical balance of forest umbrisol profiles (‘Sierra de Gata’, central western Spain)

Three techniques for obtaining soil water solutions (gravitational and matrical waters extracted using both in situ tension lysimeters and in vitro pressure chambers) and their later chemical analysis were performed in order to know the evolution of the soil‐solution composition when water moves down through the soil, from the Ah soil horizon to the BwC‐ or C‐horizons of forest soils located in western Spain. Additionally, ion concentrations and water volumes of input waters to soil (canopy washout) and exported waters (drainage solutions from C‐horizons) were determined to establish the net balance of solutes in order to determine the rates of leaching or retention of ions. A generalized process of sorption or retention of most components (even Cl^?) was observed, from the soil surface to the C‐horizon, in both gravitational and matrical waters, with H₄SiO₄, Mn²⁺, Na⁺, and SO₄^2? being the net exported components from the soil through the groundwater. These results enhance the role of the recycling effect in these forest soils. The net percentages of elements retained in these forest soils, considering the inputs and the outputs balance, were 68% K⁺, 85% Ca²⁺, 58% Mg²⁺, 7% Al³⁺, 5% Fe³⁺, 34% Zn²⁺, 57% Cl^?, and 20% NO₃^?, and about 75% of dissolved organic carbon was mineralized. Copyright © 2007 John Wiley & Sons, Ltd.     

Cation distribution in low-calcium pyroxenes: Dependence on temperature and calcium content and the thermal history of lunar and terrestrial pigeonites

Four pyroxenes with compositions En₄₈Fs₄₈Wo₄, En_47·5Fs_47·5Wo₅, En₄₅Fs₄₅Wo₁₀ and En₄₀Fs₄₀Wo₂₀, synthesized at 1200°C at atmospheric pressure, were heat-treated at 500, 600, 700, and 800°C for various lengths of time. These pyroxenes are variously ordered with respect to Fe²⁺ and Mg²⁺ without unmixing. The Fe²⁺-Mg²⁺ distribution over the two nonequivalent sites M1 and M2, determined through Mössbauer spectroscopy, is found to be a function of both temperature and concentration of Ca²⁺ at the M2 site. The preference of Fe²⁺ for the M2 site increases with decreasing temperature and increasing Ca²⁺. These data can be used to determine cation equilibration temperatures of lunar and terrestrial pigeonites. The lunar pigeonites usually indicate equilibration temperatures of 700–860°C, except the pigeonite from rock 14053, which may have been subjected to shock heating due to meteoritic impact.