Isotopic and chemical investigations on Angra dos Reis

We report on extensive isotopic studies of Pb, Sr and Xe and on chemical abundance measurements of K, Rb, Sr, Ba, Nd, Sm, U and Th for total meteorite and mineral separates of the Angra dos Reis achondrite. U-Pb, Th-Pb and Pb-Pb ages are concordant at 4.54 AE for the total meteorite and for high-purity whitlockite in Angra dos Reis. This establishes Angra dos Reis as an early planetary differentiate which has not been disturbed for these systems since 4.54 AE ago. Measured⁸⁷Sr/⁸⁶Sr in pyroxene and whitlockite for Angra dos Reis (ADOR) are distinctly below BABI by two parts in 10⁴ and only one part in 10⁴ above the lowest⁸⁷Sr/⁸⁶Sr (ALL) measured in an Allende inclusion. The difference in ADOR-ALL corresponds to an interval of condensation in the solar nebula of ～3 m.y. If²⁶Al was the heat source for the magmatism on the parent planets of Angra dos Reis and the basaltic achondrites (BABI) then the relatively large difference in⁸⁷Sr/⁸⁶Sr, BABI - ALL, must be the result of planetary evolution rather than condensation over ～10 m.y. Xe isotopic measurements confirm the presence of large amounts of²⁴⁴Pu-produced fission Xe and show that²⁴⁴Pu was enriched in the whitlockite relative to the pyroxene by a factor of ～18. We present chemical element enrichment factors between the whitlockite and the fassaitic pyroxene in Angra dos Reis. The enrichment factors demonstrate close analogy between the rare earth elements and their actinide analogs. The enrichment factor for Pu is intermediate to the enrichment factors of Nd and Sm.     

Genesis of the Angra dos Reis and other achondritic meteorites

Major, minor and trace element abundances were determined in seven Angra dos Reis samples including whole rocks, fassaite (clinopyroxene), olivine and whitlockite separates via sequential instrumental neutron activation analysis. The chondritic normalized rare earth element (REE) abundance pattern for the Angra dos Reis clinopyroxene separates shows a concave downward shape with a small negative Eu anomaly. The strong fractionation between the light and the heavy REE in olivine separates could be attributed to the presence of islands of kirschsteinite in the olivines. The large-ion lithophile trace elements were highly enriched in the whitlockite separate as expected (e.g. La ≈ 370 ppm). The lower Hf and Sc abundances in whitlockite compared to that in the equilibrium “magma” could be the result of favorable partitioning of Hf and Sc in baddeleyite, which may have crystallized prior to or with whitlockite in the interstitial liquid. Comparison of whole rock with mineral separate data shows the presence of ～3% olivine, ～2.6% spinel and small amounts of metallic Ni-Fe and troilite in the whole rock.The trace element abundances in the derivative magma from which the Angra dos Reis clinopyroxene crystallized were estimated from the clinopyroxene data and the clinopyroxene mineral-liquid partition coefficients. From the derivative magma, the trace element abundances in the possible parent magmas were calculated by assuming that these parent magmas have undergone different degrees of clinopyroxene fractional crystallization to yield the Angra dos Reis derivative magma. Using the trace element abundances in these possible parent magmas, a two-stage crystal-liquid fractionation model with source material containing olivine, orthopyroxene and clinopyroxene is presented for the genesis of Angra dos Reis. Possible combinations of the degree of equilibrium non-modal partial melting, the source mineral composition and the initial element abundances required to generate possible Angra dos Reis parent magmas are calculated by the multilinear regression analysis method. Favorable solutions for this two-stage crystal-liquid fractionation model could be that Angra dos Reis crystallized at ～70% fractional crystallization of clinopyroxene from magmas generated by reasonable degrees of equilibrium partial melting (～7–10%) of deep-seated primitive source materials (olivine ～54–30%, orthopyroxene ～33–53%, and clinopyroxene ～13–17%) with trace element (Ba, Sr, REE and Sc) abundances ～3.5–4.7 × chondrites. These calculated REE abundances in the Angra dos Reis parent body are very similar to those suggested for the primordial moon (～3–5 × chondrites).Possible genetic relationships between Angra dos Reis and other achondrites, especially cumulate eucrites and nakhlites, are studied. Apparently, the unique Angra dos Reis could not be related to those achondrites by crystal-liquid fractionation of the same parent body.     

Studies of Brazilian meteorites: III. Origin and history of the Angra dos Reis achondrite

The Angra dos Reis meteorite fell in 1869 and is a unique achondrite. It is an ultramafic igneous rock, pyroxenite, with 93% fassaite pyroxene which has 15.7% Ca-Tschermak's molecule, plus calcic olivine (Fo_53.1; 1.3% CaO), green hercynitic spinel, whitlockite (merrillite), metallic Ni-Fe, troilite, as well as magnesian kirschsteinite (Ks_62.3Mo_37.7), within olivine grains, and celsian (Cs_90.2An_7.7Ab_1.7Or_0.4) which are phases reported in a meteorite for the first time, and plagioclase (An_86.0), baddeleyite, titanian magnetite (TiO₂, 21.9%), and terrestrial hydrous iron oxide which are phases reported for the first time in this meteorite. Petrofabric analysis shows that fassaite has a preferred orientation and lineation which is interpreted as being due to cumulus processes, possibly the effect of post-depositional magmatic current flow or laminar flow of a crystalline mush. The mineral chemistry indicates crystallization from a highly silica-undersaturated melt at low pressure. Since the meteorite formed as a cumulate, pyroxene crystals may have gravitationally settled from a melt which crystallized melilite first. Plagioclase would be unstable in such a highly undersaturated melt, and feldspathoids would be rare or absent due to the very low alkali contents of the melt. The presence of rare grains of plagioclase and celsian may be the result of late-stage crystallization of residual liquids in local segregations. Thus, the Eu anomaly in Angra dos Reis may be the result of pyroxene separation from a melt which crystallized melilite earlier, rather than plagioclase as previously suggested.     

Angra dos Reis: Plutonium distribution and cooling history

The preatmospheric mass of Angra dos Reis is estimated to be about 80 kg, based on cosmic ray track densities of 1?3 × 10⁶ cm^?2 in feldspars, olivines, and pyroxenes. The²⁴⁴Pu-fission track densities in pyroxenes and adjacent olivine-feldspar track detectors, as well as in whitlockites and adjacent pyroxene-olivine detectors are about 20 and 280 × 10⁶ cm^?2 respectively. These values correspond exactly to the²⁴⁴Pu-fission xenon contents in the two minerals. This suggests an almost instantaneous cooling (>70 K per m.y.) of the Angra dos Reis material 4.55 b.y. ago. This fast cooling is the reason for a quantitative⁴He retention since that time. If the⁴He excess found in Angra dos Reis is a real effect, the source of this excess remains unknown.     

Paleomagnetism of samples from the axial zone of the Afar depression

We have studied SmNd systematics in pyroxene and phosphate mineral separates of Angra dos Reis. A pyroxene-phosphate internal isochron age ofT₂ = 4.55 ± 0.04AE is obtained, in excellent agreement with reported Pb-Pb ages.¹⁴²Nd/¹⁴⁴Nd ratios in pyroxene samples are systematically larger than those in phosphates by 6 parts in 10⁵. This variation is tentatively assigned to a radiogenic contribution from extinct¹⁴⁶Sm. Fission xenon components in pyroxene and phosphate separates are characterized by discrete ratios of fission/spallation and evidence is presented for a third ratio in celsian. It is shown that this characteristic is due to a close association of²⁴⁴Pu with the light REE. Computed ratios²⁴⁴Pu/Nd are the same in pyroxene and phosphate separates, but²⁴⁴Pu/²³⁸U and²⁴⁴Pu/²³²Th ratios are not. Taking the fission xenon retention age to be 4.55 AE, we obtain an abundance ratio²⁴⁴Pu/Nd= 1.5 × 10^?4 (or an atomic ratio²⁴⁴Pu/¹⁵⁰Nd= 1.6 × 10^?3) at this time and in the region of the solar system where the Angra dos Reis parent body formed. The exposure age of Angra dos Reis, as obtained by the⁸¹Kr-⁸³Kr method is55.5 ± 1.2m.y. Neutron capture during the 55.5-m.y. exposure to cosmic rays increased the ratio¹⁵⁰Sm/¹⁴⁹Sm in Angra dos Reis by 6 parts in 10⁴.     

High-pressure phase transformations in the system of MgSiO3-FeSiO3

Two synthetic pyroxenes (FeSiO₃, MgSiO₃) and five natural pyroxenes with compositions of about Fs₈₀En₂₀, Fs₆₀En₄₀, Fs₅₀En₅₀, Fs₄₀En₆₀, and Fs₂₀En₈₀ have been subjected to pressures up to250 ± 50kbars at a temperature of about1500 ± 200°C in a diamond anvil cell heated by an infrared laser beam. After quenching and unloading X-ray data analysis indicates that (1) those with Mg less than 50% undergo the following reactions: 2(Mg,Fe)SiO₃ (pyroxene) → (Mg,Fe)₂SiO₄ (spinel) + SiO₂ (stishovite) → 2(Mg,Fe)O (magnesiowu¨stite) + SiO₂ (stishovite) with increase of pressure, and (2) those with Mg higher than 60%, undergo the following reactions: 2(Mg,Fe)SiO₃ (pyroxene) → (Mg,Fe)₂SiO₄ (spinel) + SiO₂ (stishovite) → 2(Mg,Fe)SiO₃ (hexagonal phase) → 2(Mg,Fe)O (magnesiowu¨stite) + SiO₂ (stishovite) with increase of pressure.     

Measured oxygen fugacities of the Angra dos Reis achondrite as a function of temperature

Measurements of the oxygen fugacity (?O₂) as a function of temperature (T) were made on an interior bulk sample of the cumulate achondrite, Angra dos Reis. Data clustered between the?O₂-T relationship of the iron-wüstite assemblage and 1.2 log atm units above iron-wüstite. Interpretation of the data indicates that, throughout most of the cooling history of the meteorite, ?O₂ values were defined by equilibria involving iron-bearing species at values close to the ?O₂ of the assemblage iron-wüstite. Measured ?O₂ data are compatible with crystallization and cooling at pressures greater than 50 bars.     

Crystal-field spectra of fassaite from the Angra dos Reis meteorite

Fassaitic pyroxene from the Angra dos Reis meteorite has striking spectral properties. The⁵⁷Fe Mössbauer spectra show no Fe^3&+;, and thus the absorption is thought to originate from a complex charge-transfer process. Intense absorption at 480 nm dominates the spectrum of the meteorite and may be important in the interpretation of telescope spectra of objects in space.     

Crystal structure and compositional variation of Angra dos Reis fassaite

The crystal structure of fassaite from the Angra dos Reis meteorite has been determined by least-squares refinement of three-dimensional X-ray data to anR value of 3.3%. The pyroxene is monoclinic, space groupC2/c, with unit-cell dimensionsa = 9.738(1),b = 8.874(2),c = 5.2827(5)Å, β = 105.89(1)°, andV = 439.1(1)ų. Average bond lengths are (Si,Al)-O = 1.651, M1-O = 2.061, and M2-O = 2.489Å. The distribution of iron and magnesium between M1 and M2 suggests a temperature of equilibration greater than 1000°C.Electron microprobe analysis of several fassaite grains reveals small but statistically significant variations of (Mg + Si) versus (Al - Ti). The range of fassaite composition may be represented byEn₃Hd₂₂TiCpx₆(Di_53±2CaTs_16?2) whereEn=Mg₂Si₂O₆,Hd=CaFeSi₂O₆,TiCpx=CaTiAl₂O₆,Di=CaMgSi₂O₆,CaTs=CaAl₂SiO₆. Most fassaite analyses calculated on the basis of four cations yielded greater than six anions, suggesting that part of the titanium or chromium might be reduced to Ti³⁺ or Cr²⁺.     

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.     

The structure and sharpness of (Mg,Fe)2SiO4 phase transformations in the transition zone

To calculate accurately the pressure interval and mineral proportions (i.e. yields) across the olivine to wadsleyite and wadsleyite to ringwoodite transformations requires a detailed knowledge of the non-ideality of Fe-Mg mixing in these (Mg,Fe)₂SiO₄ solid solutions. In order to constrain the activity-composition relations that describe non-ideal mixing, Fe-Mg partitioning experiments have been conducted between magnesiowüstite and (Mg,Fe)₂SiO₄ olivine, wadsleyite and ringwoodite as a function of pressure at 1400°C. Using known activity-composition relations for magnesiowüstite the corresponding relations for the three polymorphs were determined from the partitioning data. In all experiments the presence of metallic iron ensured redox conditions compatible with the Earth’s transition zone. The non-ideality of the (Mg,Fe)₂SiO₄ solid solutions was found to decrease in the order W^wadsleyite_FeMg>W^ringwoodite_FeMg>W^olivine_FeMg. These partitioning data were used, along with published phase equilibria measurements for the Mg₂SiO₄ and Fe₂SiO₄ end-member transformations, to produce an internally consistent thermodynamic model for the Mg₂SiO₄-Fe₂SiO₄ system at 1400°C. Using this model the pressure interval of the olivine to wadsleyite transformation is calculated to be significantly smaller than previous determinations. By combining these results with Fe-Mg partitioning data for garnet, the widths of transition zone phase transformations in a peridotite composition were calculated. The olivine to wadsleyite transformation at 1400°C in dry peridotite was found to occur over a pressure interval equivalent to approximately 6 km depth and the mineral yields were found to vary almost linearly with depth across the transformation. This transformation is likely to be even sharper at higher temperatures or could be significantly broader in wet mantle or in regions with a significant vertical component of mantle flow. The entire range of estimated widths for the 410 km discontinuity (4-35 km) could, therefore, be explained by the olivine to wadsleyite transformation in a peridotite composition over a range of quite plausible mantle temperatures and H₂O contents. The wadsleyite to ringwoodite transformation in peridotite mantle was calculated to take place over an interval of 20 km at 1400°C. This transformation yield was also found to be near linear.     

The nature and significance of stacking faults in wadsleyite,natural β-(Mg,Fe)2SiO4 from the Peace River meteorite

The β-phase, spinelloid polymorph of (Mg, Fe)₂SiO₄ makes up a major part of the transition of the Earth's mantle. Naturally occurring β-(Mg, Fe)₂SiO₄ wadsleyite, from the Peace River meteorite was found to carry a variety of stacking faults, the nature of which have been studied using high resolution transmission electron microscopy. The faults lie on (010) and are generally of a complex nature, best described in terms of various stacking sequences of the component spinelloid units. The stacking faults locally transform the cation distribution, so that in the plane of the fault the structure is that of spinel. The development of such stacking faults is consequently a significant feature of the martensitic transformation of spinel to β-phase. The possible occurrence of transformation enhanced plasticity associated with this inversion is discussed, and the probable deformation mechanisms of β-(Mg, Fe)₂SiO₄ are outlined.     

Phase relations in the system LiFMgF2 at elevated pressures: Implications for the proposed mixed-oxide zone of the earth's mantle

Solvi and liquidi for various LiFMgF₂ mixtures have been determined at pressures up to 40 kbar by differential-thermal-analysis in a piston-cylinder high-pressure device. The melting curves of pure LiF and MgF₂ were also studied and the initial slopes (dT_m/dP)_{P = 0} were found to be 11.2 and 8.3°C/kbar, respectively. The eutectic composition (LiF)_0.64(MgF₂)_0.36 is independent of pressure to 35 kbar and the eutectic temperature rises approximately 6.3°C per kbar. Initial slopes of 11°C/kbar and 35°C/kbar are inferred for the melting curves of MgO and SiO₂ (stishovite) respectively, on the basis of data for their structural analogue compounds. The observed solid solution of LiF in MgF₂ and other evidence suggest the possibility of solid solution in the system (Mg,Fe)OSiO₂ (stishovite) under mantle conditions which may have important consequences for the elastic properties of a “mixed-oxide” zone of the earth's mantle.     

Impact of Ca2+ and Mg2+ on the Removal of F− by Magnesium Potassium Phosphate

This study investigates the influence of Ca²⁺ and Mg²⁺ on the removal of F^? by magnesium potassium phosphate (MPP) from water. The kinetic experiments reveal that the F^? concentration decreased from 3.5 to 3.31 mg L^?1 in a single (F^?) system and to 1.45 mg L^?1 in a ternary system (F^?, Ca²⁺, and Mg²⁺) after 1 min, respectively. Thus, the F^? removal efficiencies are found to increase by about 53% with the co‐active effect of Ca²⁺ and Mg²⁺ in the solution. Moreover, Ca²⁺ and Mg²⁺ are almost completely removed in the F^?, Ca²⁺, and Mg²⁺ system. According to the pseudo‐first‐order modeling, the rate constants k for F^?, Ca²⁺, and Mg²⁺ are 0.00348, 0.0106, and 0.0159 min^?1 respectively; thus, Mg²⁺ > Ca²⁺ > F^?. In the ternary system, the removal efficiencies are 53.29–66.03% for F^?, 99.99–100% for Ca²⁺, and 87.21–95.19% for Mg²⁺ with initial pH 5–10. The removal efficiencies of F^? increases with increases in initial concentrations of F^?, Ca²⁺, and Mg²⁺. The removal of F^? is governed by two routes: 1) adsorption by electrostatic interactions and outer sphere surface complexation; 2) co‐precipitation with Ca₃(PO₄)₂, CaHPO₄, Mg₃(PO₄)₂, and Mg(OH)₂.     

Pyroxene-garnet solid-solution equilibria in the systems Mg4Si4O12Mg3Al2Si3O12 and Fe4Si4O12Fe3Al2Si3O12 at high pressures and temperatures

Pyroxene-garnet solid-solution equilibria have been studied in the pressure range 41–200 kbar and over the temperature range 850–1,450°C for the system Mg₄Si₄O₁₂Mg₃Al₂Si₃O₁₂, and in the pressure range 30–105 kbar and over the temperature range 1,000–1,300°C for the system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂. At 1,000°C, the solid solubility of enstatite (MgSiO₃) in pyrope (Mg₃Al₂Si₃O₁₂) increases gradually to 140 kbar and then increases suddenly in the pressure range 140–175 kbar, resulting in the formation of a homogeneous garnet with composition Mg₃(Al_0.8Mg_0.6Si_0.6)Si₃O₁₂. In the MgSiO₃-rich field, the three-phase assemblage of β- or γ-Mg₂SiO₄, stishovite and a garnet solid solution is stable at pressures above 175 kbar at 1,000°C. The system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂ shows a similar trend of high-pressure transformations: the maximum solubility of ferrosilite (FeSiO₃) in almandine (Fe₃Al₂Si₃O₁₂) forming a homogeneous garnet solid solution is 40 mol% at 93 kbar and 1,000°C.If a pyrolite mantle is assumed, from the present results, the following transformation scheme is suggested for the pyroxene-garnet assemblage in the mantle. Pyroxenes begin to react with the already present pyrope-rich garnet at depths around 150 km. Although the pyroxene-garnet transformation is spread over more than 400 km in depth, the most effective transition to a complex garnet solid solution takes place at depths between 450 and 540 km. The complex garnet solid solution is expected to be stable at depths between 540 and 590 km. At greater depths, it will decompose to a mixture of modified spinel or spinel, stishovite and garnet solid solutions with smaller amounts of a pyroxene component in solution.     

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.     

Synthesis of γ-Mg2SiO4

Magnesium orthosilicate with spinel structure (γ-Mg₂SiO₄) was synthesized at about 250 kbar and 1000°C. Unit cell dimension was established to be 8.076 ± 0.001Å. X-ray powder diffraction pattern revealed a significant difference between γ-Mg₂SiO₄ and other γ-M₂SiO₄ spinels (M = Fe, Co, and Ni) in the intensities of (111) and (331) reflections, both of which are virtually absent in the Mg₂SiO₄ spinel. This feature could be thoroughly understood by the calculation of the intensities for several silicate spinels.     

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.     

Phase relations of titan-phlogopite,K2Mg4TiAl2Si6O20(OH)4: a refractory phase in the upper mantle?

Experimental data on the stability of titan-phlogopite [K₂Mg₄TiAl₂Si₆O₂₀(OH)₄] are presented which show it to be stable to substantially higher temperatures than normal phlogopite [K₂Mg₆Al₂Si₆O₂₀(OH)₄]. A qualitative model to explain the role of titan-phlogopite during magma generation is put forward. Breakdown of titan-phlogopite during melting at depth (> 150km) on subducted lithospheric slabs is believed responsible for the concomitant increase of K and Ti observed in magmas erupted during orogenic volcanism. At lower pressures (up to about 10 kbar) beneath mid-oceanic ridges, titan-phlogopite is predicted to behave as a refractory phase during partial melting in the mantle, especially if H₂O-excess conditions pertain, although at higher pressures in this environment it would almost certainly behave as a low-melting component.