Iron oxidation state in lower mantle mineral assemblages: II. Inclusions in diamonds from Kankan, Guinea

Inclusions of ferropericlase and former (Mg,Fe)(Si,Al)O₃ perovskite in diamonds from Kankan, Guinea believed to originate in the lower mantle were studied using Mössbauer spectroscopy to determine Fe³⁺/ΣFe. Fe³⁺ concentration in the (Mg,Fe)(Si,Al)O₃ inclusion is consistent with empirical relations relating Fe³⁺/ΣFe to Al concentration, supporting the inference that it crystallised in the perovskite structure at lower mantle conditions. In ferropericlase there is a nearly linear variation of trivalent cation abundance with monovalent cation abundance, suggesting a substitution of the form Na_0.5M_0.5³⁺O (M=Fe³⁺, Cr³⁺, Al³⁺). Excess positive charge is likely balanced by cation vacancies, where their abundance is observed to increase with increasing iron concentration, consistent with high-pressure experiments. The abundance of cation vacancies is related to oxygen fugacity, where ferropericlase inclusions from Kankan and São Luiz (Brazil) are inferred to have formed at conditions more oxidising than Fe-(Mg,Fe)O equilibrium, but more reducing than Re-ReO₂ equilibrium. Fe²⁺/Mg partition coefficients between (Mg,Fe)(Si,Al)O₃ and ferropericlase were calculated for inclusions co-existing in the same diamond using Mössbauer data and empirical relations based on high-pressure experimental work. Most values are consistent with high-pressure experiments, suggesting that these inclusions equilibrated at lower mantle conditions. The measured ferropericlase Fe³⁺ concentrations are consistent with diamond formation in a region of redox gradients, possibly arising from the subduction of oxidised material into reduced lower mantle. Reduction of carbonate to form ferropericlase and diamond is consistent with a slight shift of Kankan δ¹³C values to isotopically heavy compositions compared to the worldwide dataset, and could supply the oxygen necessary to satisfy the high Fe³⁺ concentration in (Mg,Fe)(Si,Al)O₃ perovskite, as well as account for the high proportion of ferropericlase in the lower mantle paragenesis. The heterogeneity of lower mantle diamond sources indicates that the composition of lower mantle diamonds do not necessarily reflect those of the bulk mantle.     

Tetrahedral occupancy of ferric iron in (Mg,Fe)O: Implications for point defects in the Earth's lower mantle

We investigated the concentration and site occupation of ferric iron (Fe³⁺) in (Mg,Fe)O to understand the influence of point defects on transport properties such as atomic diffusion, electrical conductivity and viscosity. We conducted Mössbauer spectroscopy of (Mg_0.8Fe_0.2)O single crystals synthesized at temperatures from 1673 to 2273 K and pressures from 5 to 15 GPa with Re–ReO₂ and Mo–MoO₂ oxygen fugacity buffers. The isomer shift of the Mössbauer spectra suggests that Fe³⁺ occupies mostly the tetrahedral site at reduced conditions and both the octahedral and tetrahedral sites at oxidized conditions. We formulate a thermodynamic model of point defect dissolution in (Mg,Fe)O which suggests that unassociated tetrahedral Fe³⁺ is more stable than unassociated octahedral Fe³⁺ at high-pressure and low oxygen fugacity due to the effect of configurational entropy. The pressure dependence of Fe³⁺ concentration indicates a change in the dominant site occupancy of Fe³⁺: (1) Fe³⁺ in the tetrahedral site, (2) Fe³⁺ in the octahedral site, and (3) defect clusters of Fe³⁺ and cation vacancy, in the order of increasing oxygen fugacity and decreasing pressure. This is in reasonable agreement with previously reported experiments on Fe³⁺ concentration, Mg–Fe interdiffusivity and electrical conductivity. We consider it plausible that (Mg,Fe)O accommodates Fe³⁺ in the tetrahedral site down to the lower mantle. Based on our results and available experimental data, we discuss the solubility competition between Fe³⁺ and protons (H⁺), and its implications for transport properties in the lower mantle.     

Elasticity of (Mg, Fe)(Si, Al)O3-perovskite at high pressure

The most abundant mineral on Earth has a perovskite crystal structure and a chemistry that is dominated by MgSiO₃ with the next most abundant cations probably being aluminum and ferric iron. The dearth of experimental elasticity data for this chemically complex mineral limits our ability to calculate model seismic velocities for the lower mantle. We have calculated the single crystal elastic moduli (c_ij) for (Mg, Fe^3 +)(Si, Al)O₃ perovskite using density functional theory in order to investigate the effect of chemical variations and spin state transitions of the Fe³⁺ ions. Considering the favored coupled substitution of Mg²⁺-Si^4 + by Fe³⁺-Al³⁺, we find that the effect of ferric iron on seismic properties is comparable with the same amount of ferrous iron. Ferric iron lowers the elastic moduli relative to the Al charge-coupled substitution. Substitution of Fe³⁺ for Al³⁺, giving rise to an Fe/Mg ratio of 6%, causes 1.8% lower longitudinal velocity and 2.5% lower shear velocity at ambient pressure and 1.1% lower longitudinal velocity and 1.8% lower shear velocity at 142 GPa. The spin state of the iron for this composition has a relatively small effect (< 0.5% variation) on both bulk modulus and shear modulus.     

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.     

Ab initio study of the composition dependence of the pressure-induced spin crossover in perovskite (Mg1 − x,Fex)SiO3

We present ab initio calculations of the zero-temperature iron high- to low-spin crossover in (Mg_1 ? xFe_x)SiO₃ perovskite at pressures relevant to Earth's lower mantle. Equations of state are fit for a range of compositions and used to predict the Fe spin transition pressure and associated changes in volume and bulk modulus. We predict a dramatic decrease in transition pressure as Fe concentration increases. This trend is contrary to that seen in ferropericlase, and suggests the energetics for spin crossover is highly dependent on the structural environment of Fe. Both Local Density Approximation (LDA) and Generalized Gradient Approximation (GGA) exchange-correlation methods are used, and both methods reproduce the same compositional trends. However, GGA gives a significantly higher transition pressure than LDA. The spin transition is made easier by the decreasing spin-flip energy with pressure but is also driven by the change in volume from high to low spin. Volume trends show that high-spin Fe²⁺ is larger than Mg²⁺ even under pressure, but low-spin Fe²⁺ is smaller at ambient conditions and approximately the same size as Mg²⁺ under high pressure, indicating that low-spin Fe²⁺ is less compressible than high-spin Fe²⁺. We find large changes between high- and low-spin in the slope of volume with Fe concentration. Although these changes are small in absolute magnitude for small Fe content, they are still important when measured per Fe and could be relevant for calculating partitioning coefficients in the lower mantle.     

Hematite spherules in basaltic tephra altered under aqueous, acid-sulfate conditions on Mauna Kea volcano, Hawaii: Possible clues for the occurrence of hematite-rich spherules in the Burns formation at Meridiani Planum, Mars

Iron-rich spherules (> 90% Fe₂O₃ from electron microprobe analyses) ∼10-100 μm in diameter are found within sulfate-rich rocks formed by aqueous, acid-sulfate alteration of basaltic tephra on Mauna Kea volcano, Hawaii. Although some spherules are nearly pure Fe, most have two concentric compositional zones, with the core having a higher Fe / Al ratio than the rim. Oxide totals less than 100% (93-99%) suggest structural H₂O and/or OH^− 1. The transmission Mössbauer spectrum of a spherule-rich separate is dominated by a hematite (α-Fe₂O₃) sextet whose peaks are skewed toward zero velocity. Skewing is consistent with Al³⁺ for Fe³⁺ substitution and structural H₂O and/or OH^− 1. The grey color of the spherules implies specular hematite. Whole-rock powder X-ray diffraction spectra are dominated by peaks from smectite and the hydroxy sulfate mineral natroalunite as alteration products and plagioclase feldspar that was present in the precursor basaltic tephra. Whether spherule formation proceeded directly from basaltic material in one event (dissolution of basaltic material and precipitation of hematite spherules) or whether spherule formation required more than one event (formation of Fe-bearing sulfate rock and subsequent hydrolysis to hematite) is not currently constrained. By analogy, a formation pathway for the hematite spherules in sulfate-rich outcrops at Meridiani Planum on Mars (the Burns formation) is aqueous alteration of basaltic precursor material under acid-sulfate conditions. Although hydrothermal conditions are present on Mauna Kea, such conditions may not be required for spherule formation on Mars if the time interval for hydrolysis at lower temperatures is sufficiently long.     

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.     

X-ray study and mössbauer spectroscopy on lunar ilmenites (Apollo 11)

A comparison of lunar ilmenites (Apollo 11, 10047, 13) with terrestrial ilmenites by means of electron microprobe analysis, X-ray and Mössbauer spectrometry showed that the lunar samples contained no Fe³⁺ but excess Ti³⁺. This causes an increase of thec-axis as compared with stoichiometric ilmenite.     

A laboratory study of meteor smoke analogues: Composition, optical properties and growth kinetics

Meteoric smoke forms in the mesosphere from the recondensation of the metallic species and silica produced by meteoric ablation. A photochemical flow reactor was used to generate meteoric smoke mimics using appropriate photolytic precursors of Fe and Si atoms in an excess of oxidant. The following systems were studied: (i) Fe+O₃/O₂, (ii) Fe+O₃/O₂+H₂O, (iii) Fe+Si/SiO+O₃/O₂ and (iv) Si/SiO+O₃/O₂. The resulting nano-particles were captured for imaging by transmission electron microscopy, combined with elemental analysis using X-ray (EDX) and electron energy loss (EELS) techniques. These systems generated particle compositions consistent with: (i) Fe₂O₃ (hematite), (ii) FeOOH (goethite), (iii) Fe₂SiO₄ (fayalite) and (iv) SiO₂ (silica). Electron diffraction revealed that the Fe-containing particles were entirely amorphous, while the SiO₂ particles displayed some degree of crystallinity. The Fe-containing particles formed fractal aggregates with chain-like morphologies, whereas the SiO₂ particles were predominantly spherical and compact in appearance. The optical extinction spectra of the Fe-containing particles were measured from 300 nm<λ<650 nm. Excellent agreement was found with the extinction calculated from Mie theory using the refractive indices for the bulk compounds, and assuming that the fractal aggregates are composed of poly-disperse distributions of constituent particles with radii ranging from 5 to 100 nm. These sizes were confirmed from measurements of the particle size distributions and microscopic imaging. Finally, the particle growth kinetics of the Fe-containing systems exhibit unexpectedly rapid agglomerative coagulation. This was modelled by assuming an initial period of coalescent particle growth resulting from diffusional (Brownian) coagulation to form primary particles; further growth of these particles is then dominated by long-range magnetic dipole–dipole interactions, leading to the fractal aggregates observed. The atmospheric implications of this work are then discussed.     

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.     

Chrome spinel in normal MORB‐type greenstones from the Paleozoic–Mesozoic Mino terrane,East Takayama area,central Japan: Crystallization course with a U‐turn

Phenocrystic chrome spinel crystallized in normal MORB‐type greenstones in the East Takayama area. Associated phenocryst minerals show a crystallization sequence that was olivine first, followed by plagioclase, and finally clinopyroxene. Chrome spinel ranges from 0.54 to 0.77 in Mg/(Mg+Fe²⁺) and 0.21 to 0.53 in Cr/(Cr+Al); the Fe³⁺ content varies from 0.07 to 0.22 p.f.u. (O = 4). Significant compositional differences of spinel were observed among the phenocryst mineral assemblages. Chrome spinel in the olivine–spinel assemblage shows a wide range in Cr/(Cr+Al), and is depleted in Fe²⁺ and Fe³⁺. Chrome spinel in the olivine–plagioclase–clinopyroxene–spinel assemblage is Fe²⁺‐ and Fe³⁺‐rich at relatively high Cr/(Cr+Al) ratios. Basalt with the olivine–plagioclase–spinel assemblage contains both aluminous spinel and Fe²⁺‐ and Fe³⁺‐rich spinel. The assumed olivine–spinel equilibrium suggests that chrome spinel in the olivine–spinel assemblage changed in composition from Cr‐ and Fe²⁺‐rich to Al‐ and Mg‐rich with the progress of fractional crystallization. Chrome spinel in the olivine–plagioclase–clinopyroxene–spinel assemblage, on the other hand, exhibits the reversed variations in Mg/(Mg+Fe²⁺) and in Cr/(Cr+Al) ratios that decrease and increase with the fractional crystallization, respectively. The entire crystallization course of chrome spinel, projected onto the Mg/(Mg+Fe²⁺)–Cr/(Cr+Al) diagram, exhibits a U‐turn, and appears to be set on a double‐lane route. The U‐turn point lies in the compositional field of chrome spinel in the olivine–plagioclase–spinel assemblage, and may be explained by plagioclase fractionation that began during the formation of the olivine–plagioclase–spinel assemblage.     

Orthorhombic perovskite phases observed in olivine,pyroxene and garnet at high pressures and temperatures

Ferromagnesian silicate olivines, pyroxenes and garnets with Mg/(Mg + Fe)?0.3 (molar) have been found to transform to high-pressure phases characterized by the orthorhombic perovskite structure when compressed to pressures above 250 kbar in a diamond-anvil press and heated to temperatures above 1,000°C with a YAG laser. The zero-pressure density of the perovskite phase of (Mg,Fe)SiO₃ is about 3–4% greater than that of the close-packed oxides, rocksalt plus stishovite. For (Mg,Fe)₂SiO₄ compounds, the perovskite plus rocksalt phase assemblage is 2–3% denser than the mixed oxides. The experimental synthesis of such high-density perovskite phases in olivine, pyroxene and garnet compounds suggests that (Mg,Fe)SiO₃-perovskite is the dominant mineral phase in the earth's lower mantle.     

The Apure River: geochemistry of major and selected trace elements in an Orinoco River tributary coming from the Andes,Venezuela

The analysis of physicochemical variables and selected dissolved elements was performed on the Apure River waters for 15 months. The variables pH, alkalinity, dissolved O₂, conductivity and Na, Ca, Mg and Cd concentrations showed maximum values during low water, whereas K, Si, Fe, Al, Mn, Zn, Cu, Cr and dissolved organic carbon (DOC) showed maximum concentrations during rising and high water. Five important factors were found to control the amount and temporal variability of the dissolved elements: lithology, hydrology, vegetation–floodplain processes, redox conditions and organic complexation. Weathering of silicates, carbonates and evaporites in the Andes provides most of the proportion of Na, Ca, Mg and HCO₃^? to waters. The temporal variability of these ions is controlled by a dilution process. Although Si can be taken up by the biomass, Si and K can be leached from the floodplain by weathering of clays. Microbial decay of the submerged plants in the floodplain during the inundation periods provides DOC and K to river waters and changes the redox conditions in water. The changing redox conditions control the solubility of Mn, Zn and Fe. Dissolved Mn is a function of pH‐dependent redox process, whereas Zn solubility is controlled by scavenging of Zn during the oxidation of Mn²⁺ to MnO₂. Positive relationships between Al, Fe, Cu, Cr and DOC suggest that these elements are complexed by organic colloids generated in the floodplain. Moreover, the binding capacity of Fe with DOC increases under reducing conditions. Although Cd seems to be provided by weathering in the Andes, several processes can affect the mobility of Cd during transport. Copyright © 2010 John Wiley & Sons, Ltd.     

Rhonite in molten inclusions from the olivine of allivalite nodules from Malyi Semyachik Volcano and basalts of Klyuchevskoi Volcano,Kamchatka

A microprobe study of olivine found in allivalite nodules from lavas discharged by Malyi Semyachik Volcano and of olivine phenocrysts from basalts discharged by Klyuchevskoi Volcano revealed the presence of rhonite as a daughter mineral, for the first time ever. Rhonite was found in small (10–50 μm) grains that are xenomorphic in intergrowths with other minerals and have regular crystallographic outlines in contact with glass. We also found high-alumina clinopyroxene, chromium-free spinel, and hornblende. Residual glass is distinguished by its higher concentrations of SiO₂, Al₂O₃, alkalies, and by lower concentrations of FeO, MgO, and CaO. The chemical composition of the rhonite we studied is characterized by limited variations of the major components and fits the formula (Si,Al)₆(Ti,Al,Fe⁺³,Fe⁺²,Mn,Mg)₆(Ca,Na)₂O₂₀ well. The data points in the composition of the rhonites we have studied lie in the overall field of much more variable compositions to be found in the field. Unlike the previous findings in alkaline and subalkaline rocks, the rhonite we describe in the present report was found in rocks of the tholeiitic and calc-alkaline series.     

Stability relations of ilmenite and ulvöspinel in the Fe-Ti-O system and application of these data to lunar mineral assemblages

The fO₂ stability relations of ilmenite and ulvöspinel were determined using C-O H-N gas-flow apparatus with fO₂ measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. For Fe+TiO₂ + 1/2 O₂ =FeTiO₃ (from 850°–1050°C), 1/2 log fO₂=(−11,250/T) + 0.98 and for Fe+FeTiO₃ + 1/2 O₂ =Fe₂TiO₄ (from 850°–1210°C), 1/2 logfO₂ = (−12,170/T) + 1.93. These curves lie at significantly higher values of ?O₂ than determined by previous investigators (i.e., 3/4 and1/4 order of magnitude for ilmenite and ulvöspinel, respectively). In addition, for Fe+ 2TiO₂ + 1/2 O₂ =FeTi₂O₅ (1210°C), ΔG_r⁰=−45.8 ± 0.6 kcal. The QFI curve crosses the ulvöspinel reduction curve at ∼950°C and is at lower values of fO₂ below this temperature. The occurrences of fayalite reduction to SiO₂ + Fe in lunar rock 14053, as well as a new finding of this assemblage in 14072, are evidence for extreme sub-solidus reduction, whereas ulvöspinel breakdown alone occurs under less reducing conditions. The ‘complete’ reduction of ulvöspinel to TiO₂ + Fe occurs in 2 steps: first, to ilmenite + Fe and then, however more slowly, to rutile + Fe. Thus, the presence of ulvöspinel but lack of ilmenite reduction in lunar rocks cannot be used as evidence that the fO₂ was between the associated curves — only upper limits of fO₂ can be inferred.     

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.     

Oxygen isotope fractionation in mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of¹⁸O-enrichment:pyroxene (Mg, Fe, Ca)₂Si₂O₆>olivine (Mg, Fe)₂SiO₄ > spinel (Mg, Fe)₂SiO₄> ilmenite (Mg, Fe, Ca) SiO₃>perovskite (Mg, Fe, Ca) SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) System are in excellent agreement with the experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth’s interior can be described by the following sequence of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

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.     

Spin state of ferric iron in MgSiO3 perovskite and its effect on elastic properties

Recent studies have indicated that a significant amount of iron in MgSiO₃ perovskite (Pv) is Fe³⁺ (Fe³⁺/ΣFe = 10–60%) due to crystal chemistry effects at high pressure (P) and that Fe³⁺ is more likely than Fe²⁺ to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Mössbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe³⁺ in the laser-heated diamond-anvil cell to over 100 GPa. Fe³⁺ increases the anisotropy of the Pv unit cell, whereas Fe²⁺ decreases it. In Pv synthesized above 50 GPa, Fe³⁺ enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50–60 GPa where all Fe³⁺ in the B site becomes LS, while Fe³⁺ in the A site remains HS to at least 136 GPa. Fe³⁺ makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50–60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe³⁺.     

The influence of oxidation state on the electrical conductivity of olivine

The electrical conductivity of a single crystal of San Carlos olivine (Fo₉₂, 0.16 wt.% Fe₂O₃) has been measured as a function of temperature and oxygen fugacity (fO₂). After heating to 1338°C at fO₂ = 10^?12 atm., the conductivity at 950°C was 10^?5 (ohm-m)^?1, almost 3 orders of magnitude less than that measured in air. This decrease is due to the reduction of Fe³⁺ to Fe²⁺. Further heating to 1500°C at fO₂ = 10^?14 atm., decreased the electrical conductivity at 950°C to 10^?6 (ohm-m)^?1. When recovered at room temperature, the speciment had Fo₉₆ composition and contained small, opaque blebs distributed throughout the crystal. Derivations of temperature profiles for the earth's mantle from conductivity-depth models must take account of the important role played by iron oxidation state in the electrical conductivity of olivine.