A new high-pressure phase of Ca2Al2SiO7 and implications for the earth''s interior

Gehlenite (Ca₂Al₂SiO₇) has been found to transform to a new phase at pressures greater than 100 kbar and at about 1000°C, using a diamond-anvil pressure cell coupled with laser heating. The atoms of the new phase appear to be arranged in a perovskite-related structure similar to that described for Na₂Ti₃O₇. The structure probably consists of layers of (Al₂SiO₇)⁴⁻, which are built up from blocks of edge-sharing (Al, Si)O₆ octahedra and these blocks are joined by common octahedra corners. A small cubic unit cell with a = 3.719 ± 0.004 Å indexes completely the strong lines of the powder diffraction pattern, and a superlattice with a = 14.88 ± 0.02 Å satisfies all the observed weak lines in addition to the strong ones. However, the cell may be pseudocubic. The small cell contains a half of the gehlenite formula while the large cell contains 32 gehlenite formulae. Hence the molar volume for the new phase of Ca₂Al₂SiO₇ is calculated to be 61.96 ± 0.20 cm³ at atmospheric pressure and room temperature. The new sodium titanate-type structure is probably more closely packed than an ordinary perovskite-type structure in which all octahedral corners are shared. This view is strongly supported by the very great density of this new phase, which is about 8% denser than the equivalent mixture of CaAl₂O₄ (calcium ferrite type) plus CaSiO₃ (cubic perovskite type). The new phase is probably the most closely packed silicate known. Mg₂SiO₄ (spinel) was found to transform to an assemblage containing MgSiO₃ (perovskite) plus MgO (periclase) at P-T conditions equivalent to the upper part of the lower mantle. By reacting with MgO, the perovskite modification of both MgSiO₃ and MgSiO₃ · xAl₂O₃ may adopt the sodium titanate structure at the still greater depths of the lower mantle. If the sodium titanate structures of Mg₂(Al₂Si)O₇ and Mg₂(MgSi₂)O₇ are present in the deep part of the lower mantle, MgO does not exist as a separate phase at the mantle-core boundary. This might be an obstacle to the possibility of dissolving these oxides (specifically the FeO component) in the molten Fe in the outer core as suggested by geophysical and geochemical studies of the earth's interior. The mechanism for developing the chemical plumes in the deep mantle proposed by Anderson does not appear to be consistent with studies of phase transformations in Ca-Al-rich compounds as outlined in this paper.     

Phase transition in CaSiO3 perovskite

A phase transition in pure CaSiO₃ perovskite was investigated at 27 to 72 GPa and 300 to 819 K by in-situ X-ray diffraction experiments in an externally-heated diamond-anvil cell. The results show that CaSiO₃ perovskite takes a tetragonal form at 300 K and undergoes phase transition to a cubic structure above 490–580 K in a pressure range studied here. The transition boundary is strongly temperature-dependent with a slightly positive dT / dP slope of 1.1 (± 1.3) K/GPa. It is known that the transition temperature depends on Al₂O₃ content dissolved in CaSiO₃ perovskite [Kurashina et al., Phys. Earth Planet. Inter. 145 (2004) 67–74]. The phase transition in CaSiO₃(+ 3 wt.% Al₂O₃) perovskite therefore could occur in a cold subducted mid-oceanic ridge basalt (MORB) crust at about 1200 K in the upper- to mid-lower mantle. This phase transition is possibly ferroelastic-type and may cause large seismic anomalies in a wide depth range.     

The energetics of aluminum solubility into MgSiO3 perovskite at lower mantle conditions

Experiments [T. Irifune (1994) Nature 370, 131–133; E. Ito et al. (1998) Geophys. Res. Lett. 25, 821–824; A. Kubo, M. Akaogi (2000) Phys. Earth Planet. Int. 121, 85–102] indicate that (Mg,Fe)SiO₃ perovskite, commonly believed to be the most abundant mineral in the Earth, is the preferred host phase of Al₂O₃ in the Earth’s lower mantle. Aiming to better understand the effects of Al₂O₃ on the thermoelastic properties of the lower mantle, we use atomistic models to examine the chemistry and elasticity of solid solutions within the MgSiO₃(perovskite)–Al₂O₃(corundum)–MgO(periclase) mineral assemblage under conditions pertinent to the lower mantle: low Al cation concentrations, P=25–100 GPa, and T=1000–2000 K. We assess the relative stabilities of two likely substitution mechanisms of Al into MgSiO₃ perovskite in terms of reactions involving MgSiO₃, MgO, and Al₂O₃, in a manner similar to the 0 Kelvin calculations of Brodholt [J.P. Brodholt (2000) Nature 407, 620–622] and Yamamoto et al. [T. Yamamoto et al. (2003) Earth Planet. Sci. Lett. 206, 617–625]. We determine the equilibrium composition of the assemblage by examining the chemical potentials of the Al₂O₃ and MgO components in solid solution with MgSiO₃, as functions of concentration. We find that charge coupled substitution dominates at lower mantle pressures and temperatures. Oxygen vacancy-forming substitution accounts for 3–4% of Al substitution at shallow lower mantle conditions, and less than 1% in the deep mantle. For these two pressure regimes, the corresponding adiabatic bulk moduli of aluminous perovskite are 2% and 1% lower than that of pure MgSiO₃ perovskite.     

Element partitioning between magnesium silicate perovskite and ferropericlase: New insights into bulk lower-mantle geochemistry

In this study, we investigated iron–magnesium exchange and transition-metal trace-element partitioning between magnesium silicate perovskite (Mg,Fe)SiO₃ and ferropericlase (Mg,Fe)O synthetised under lower-mantle conditions (up to 115 GPa and 2200 K) in a laser-heated diamond anvil cell. Recovered samples were thinned to electron transparency by focused ion beam and characterized by analytical transmission electron microscopy (ATEM) and nanometer-scale secondary ion mass spectroscopy (nanoSIMS). Iron concentrations in both phases were obtained from X-ray energy dispersive spectroscopy measurements and nanoSIMS. Our results are the first to show that recently reported spin-state and phase transitions in the lower mantle directly affect the evolution of Fe–Mg exchange between both phases. Mg-perovskite becomes increasingly iron-depleted above 70–80 GPa possibly due to the high spin–low spin transition of iron in ferropericlase. Conversely, the perovskite to post-perovskite transition is accompanied by a strong iron enrichment of the silicate phase, ferropericlase remaining in the Fe-rich phase though. Nanoparticles of metallic iron were observed in the perovskite-bearing runs, suggesting the disproportionation of ferrous iron oxide, but were not observed when the post-perovskite phase was present. Implications on the oxidation state of the Earth and core segregation will be discussed. Transition trace-element (Ni, Mn) concentrations (determined with the nanoSIMS) show similar trends and could thus be used to trace the origin of diamonds generated at depth. This study provides new results likely to improve the geochemical and geophysical models of the Earth's deep interiors.     

The equation of state of CaSiO3 perovskite to 108 GPa at 300 K

Pressure–volume measurements have been performed for CaSiO₃ perovskite to 108 GPa at 300 K using NaCl and argon pressure-transmitting media, and energy dispersive X-ray diffraction (EDXD) in a diamond-anvil cell (DAC). By determining a parameter that is the product of the elastic anisotropy, S, and the uniaxial stress component, t, for each data point, we define the stress condition of the sample. For different points at the same pressure in a temperature-quenched sample, the St value can differ by as much as a factor of 5, indicating heterogeneity in the stress condition. This may be responsible for the large scatter of earlier P–V measurements in the DAC which in general used a large diameter X-ray beam. Also, the St value provides insight into the elastic anisotropy, S, of CaSiO₃ perovskite and platinum. The sign of S (positive) for CaSiO₃ perovskite agrees with first principles calculations but the magnitude may be inconsistent. A new compression curve at 300 K was obtained for CaSiO₃ perovskite by using those data points which represent the most nearly hydrostatic conditions. It is observed that the data points with high St values yield larger volumes than the points with small St values at a given pressure. By selecting the data points having low St values (St≤0.005), combining with lower pressure large volume press (LVP) measurements and fitting to third order Birch–Murnaghan equation of state (EOS), we find that CaSiO₃ perovskite is more compressible (V₀=45.58±0.05 ų, K_T0=236±4 GPa, and K_T0′=3.9±0.2 GPa) than suggested by previous studies. The density and bulk modulus of CaSiO₃ perovskite at lower mantle pressures and 300 K are 1–3% greater and 5–15% smaller, respectively, than found in previous studies. This study demonstrates that defining the stress state of the sample is crucial to obtain an accurate 300 K compression curve for unquenchable high-pressure phases.     

Silicate perovskite analogue ScAlO3: temperature dependence of elastic moduli

The elastic moduli of ScAlO₃ perovskite, a very close structural analogue for MgSiO₃ perovskite, have been measured between 300 and 600 K using high precision ultrasonic interferometry in an internally heated gas-charged pressure vessel. This new capability for high temperature measurement of elastic wave speeds has been demonstrated on polycrystalline alumina. The temperature derivatives of elastic moduli of Al₂O₃ measured in this study agree within 15% with expectations based on published single-crystal data. For ScAlO₃ perovskite, the value of (∂K_S/∂T)_P is −0.033 GPa K⁻¹ and (∂G/∂T)_P is −0.015 GPa K⁻¹. The relative magnitudes of these derivatives agree with the observation in Duffy and Anderson [Duffy, T.S., Anderson, D.L., 1989. Seismic velocities in mantle minerals and the mineralogy of the upper mantle. J. Geophys. Res. 94, 1895–1912.] that |(∂K_S/∂T)_P| is typically about twice |(∂G/∂T)_P|. The value of (∂K_S/∂T)_P for ScAlO₃ is intermediate between those inferred less directly from V(P,T) studies of Fe-free and Fe- and Al-bearing MgSiO₃ perovskites [Wang, Y., Weidner, D.J., Liebermann, R.C., Zhao, Y., 1994. P–V–T equation of state of (Mg,Fe)SiO₃ perovskite: constraints on composition of the lower mantle. Phys. Earth Planet. Inter. 83, 13–40; Mao, H.K., Hemley, R.J., Shu, J., Chen, L., Jephcoat, A.P., Wu, Y., Bassett, W.A., 1991. Effect of pressure, temperature and composition on the lattice parameters and density of (Mg,Fe) SiO₃ perovskite to 30 GPa. J. Geophys. Res. 91, 8069–8079; Zhang, Weidner, D., 1999. Thermal equation of state of aluminum-enriched silicate perovskite. Science 284, 782–784]. The value of |(∂G/∂T)|_P for ScAlO₃ is similar to those of most other mantle silicate phases but lower than the recent determination for MgSiO₃ perovskite [Sinelnikov, Y., Chen, G., Neuville, D.R., Vaughan, M.T., Liebermann, R.C., 1998. Ultrasonic shear wave velocities of MgSiO₃ perovskite at 8 GPa and 800K and lower mantle composition. Science 281, 677–679].

Combining the results from the previous studies and current measurements on ScAlO₃ perovskite, we extracted the parameters (q and γ₀) needed to fully specify its Mie–Grüneisen–Debye equation-of-state. In this study, we have demonstrated that acoustic measurements of K_S(T), unlike V(P,T) data, tightly constrain the value of q. It is concluded that ScAlO₃ has ‘normal’ γ₀ (1.3) and high q (3.6). The high value of q indicates that ScAlO₃ has very strong intrinsic temperature dependence of the bulk modulus; similar behaviour has been observed in measurements on Fe- and Al-bearing silicate perovskites (Mao et al., 1991; Zhang and Weidner, 1999).     

Low-degree partial melting trends recorded in upper mantle minerals

The study of glass inclusions inside mantle minerals provides direct information about the chemistry of naturally occurring mantle-derived melts and the fine-scale complexity of the melting process responsible for their genesis. Minerals in a spinel lherzolite nodule from Grande Comore island contain glass inclusions which, after homogenization by heating, exhibit a continuous suite of chemical compositions clearly distinct from that of the host basanitic lava. The compositions range from silicic, with nepheline–olivine normative, 64 wt% SiO₂ and 11 wt% alkali oxides, to almost basaltic, with quartz normative, 50 wt% SiO₂ and 1–2 wt% alkali oxides. Within a single mineral phase, olivine, the inferred primary melt composition varies from 54 to 64 wt% SiO₂ for MgO content ranging from 8 to 0.8 wt%. An experimental study of the glass and fluid inclusions indicates that trapped melts represent liquids that are in equilibrium with their host phases at moderate temperature and pressure (T≈1230°C and P≈1.0 Gpa for melts trapped in olivine). Quantitative modelling of the compositional trends defined in the suite shows that all of the glasses are part of a cogenetic set of melts formed by fractional melting of spinel lherzolite, with F varying between 0.2 and 5%. The initial highly silicic, alkali-rich melts preserved in Mg-rich olivine become richer in FeO, MgO, CaO and Cr₂O₃ and poorer in SiO₂, K₂O, Na₂O, Al₂O₃ and Cl with increasing melt fractions, evolving toward the basaltic melts found in clinopyroxene. These results confirm the connection between glass inclusions inside mantle minerals and partial mantle melts, and indicate that primary melts with SiO₂ >60 wt%, alkali oxides >11%, FeO <1 wt% and MgO <1 wt% are generated during incipient melting of spinel peridotite. The composition of the primary melts is inferred to be dependent on pressure, and to reflect both the speciation of dissolved CO₂ and the effect of alkali oxides on the silica activity coefficient in the melt. At pressures around 1 GPa, low-degree melts are characterized by alkali and silica-rich compositions, with a limited effect of dissolved CO₂ and a decreased silica activity coefficient caused by the presence of alkali oxides, whereas at higher pressures alkali oxides form complexes with carbonates and, consequently, alkali-rich silica-poor melts will be generated.     

橄榄石成核动力学方程的修正及其对动力学数据的约束

本文从成核动力学理论出发,考虑新相晶核的表面能对其形状的影响,修正了晶面成核情形的成核动力学方程.新的成核率方程还原了传统成核率方程中通常简化为常数的指前系数.结合修正的相变体积分数计算公式,新的成核率方程可以确定出成核过程中的两个物理参量:新相晶粒与反应相晶粒的接触角度及新相物质与反应相物质之间的表面能.分析结果表明...     

Fe isotope fractionation in iron meteorites: New insights into metal-sulphide segregation and planetary accretion

Magmatic iron meteorites are considered to be remnants of the metallic cores of differentiated asteroids, and may be used as analogues of planetary core formation. The Fe isotope compositions (δ^57/54Fe) of metal fractions separated from magmatic and non-magmatic iron meteorites span a total range of 0.39‰, with the δ^57/54Fe values of metal fractions separated from the IIAB irons (δ^57/54Fe 0.12 to 0.32‰) being significantly heavier than those from the IIIAB (δ^57/54Fe 0.01 to 0.15‰), IVA (δ^57/54Fe − 0.07 to 0.17‰) and IVB groups (δ^57/54Fe 0.06 to 0.14‰). The δ^57/54Fe values of troilites (FeS) separated from magmatic and non-magmatic irons range from − 0.60 to − 0.12‰, and are isotopically lighter than coexisting metal phases. No systematic relationships exist between metal-sulphide fractionation factor (Δ^57/54Fe_M-FeS = δ^57/54Fe_metal − δ^57/54Fe_FeS) metal composition or meteorite group, however the greatest Δ^57/54Fe_M-FeS values recorded for each group are strikingly similar: 0.79, 0.63, 0.76 and 0.74‰ for the IIAB, IIIAB, IAB and IIICD irons, respectively. Δ^57/54Fe_M-FeS values display a positive correlation with kamacite bandwidth, i.e. the most slowly-cooled meteorites, which should be closest to diffusive equilibrium, have the greatest Δ^57/54Fe_M-FeS values. These observations provide suggestive evidence that Fe isotopic fractionation between metal and troilite is dominated by equilibrium processes and that the maximum Δ^57/54Fe_M-FeS value recorded (0.79 ± 0.09‰) is the best estimate of the equilibrium metal-sulphide Fe isotope fractionation factor. Mass balance models using this fractionation factor in conjunction with metal δ^57/54Fe values and published Fe isotope data for pallasites can explain the relatively heavy δ^57/54Fe values of IIAB metals as a function of large amounts of S in the core of the IIAB parent body, in agreement with published experimental work. However, sequestering of isotopically light Fe into the S-bearing parts of planetary cores cannot explain published differences in the average δ^57/54Fe values of mafic rocks and meteorites derived from the Earth, Moon and Mars and 4-Vesta. The heavy δ^57/54Fe value of the Earth's mantle relative to that of Mars and 4-Vesta may reflect isotopic fractionation due to disproportionation of ferrous iron present in the proto-Earth mantle into isotopically heavy ferric iron hosted in perovskite, which is released into the magma ocean, and isotopically light native iron, which partitions into the core. This process cannot take place at significant levels on smaller planets, such as Mars, as perovskite is only stable at pressures > 23 GPa. Interestingly, the average δ^57/54Fe values of mafic terrestrial and lunar samples are very similar if the High-Ti mare basalts are excluded from the latter. If the Moon's mantle is largely derived from the impactor planet then the isotopically heavy signature of the Moon's mantle requires that the impacting planet also had a mantle with a δ^57/54Fe value heavier than that of Mars or 4-Vesta, which then implies that the impactor planet must have been greater in size than Mars.     

Focused ion beam technique and transmission electron microscope studies of microdiamonds from the Saxonian Erzgebirge, Germany

A focused ion beam of Ga ions is a relatively new technique that has been developed for microelectronic industries. Now researchers of the Earth sciences find it to be a promising tool for studying various geological materials. Using the FIB technique and an FEI Strata DB 235 dual beam system, we have successfully prepared several electron-transparent foils, which crossed μm-sized diamonds included in host minerals such as zircon and garnet from quartzofeldspathic rocks of the Saxonian Erzgebirge, Germany. Scanning and transmission electron microscopy applied to these foils revealed that the diamonds contain crystalline nanometric inclusions. These inclusions consist of minerals of known stoichiometries such as SiO₂ and Al₂SiO₅, whereas others are characterized by different combinations of Si, K, P, Ti, and Fe in the presence of oxygen (stoichiometries are not clear at this stage of research). One suite of inclusions is assumed to be represented by archerite, KH₂PO₄, which is known to be stable at pressures of 4–22 GPa, and one nanocrystal containing Pb, oxygen and carbon is interpreted to be Pb_xO_y or PbCO₃. Along with solid crystalline inclusions, the diamonds contain cavities filled by liquid/gas that escaped during sample preparation. These are associated with dislocations of diamond growth. Our data are consistent with the concept of diamond crystallization from a COH-rich multicomponent supercritical fluid and suggest that the composition of such a fluid is more consistent with a local crustal source rather than that of a mantle origin.     

The wetting ability of Si-bearing liquid Fe-alloys in a solid silicate matrix—percolation during core formation under reducing conditions?

The wetting characteristics of liquid Fe–Si alloys in a matrix of the respective predominating stable silicate mantle mineral (forsterite or silicate perovskite) at pressures of 2–5 and 25 GPa and temperatures of 1600–2000 °C were studied by determining the liquid metal–solid silicate contact angles. The median angle values from texturally equilibrated samples were found to be independent of pressure, temperature, silicate mineralogy and the Si content in the metal fraction and range between 130° and 140° which is far above the critical wetting boundary of 60°. This shows that within the studied range of conditions dissolved Si does not lower the surface energies between Fe-rich liquids and silicate mantle grains. As a consequence, under reducing conditions the presence of Si in the metal phase of planetary bodies would not have enhanced percolative flow as an effective metal–silicate separation process.     

Melting of β-quartz up to 2.0 GPa and thermodynamic optimization of the silica liquidus up to 6.0 GPa

Melting relations of β-quartz were experimentally determined at 1.0 GPa (1900±20 °C), 1.5 GPa (2033±20 °C), and 2.0 GPa (2145±20 °C) using a new high-pressure assembly in a piston–cylinder apparatus and substantial differences were found with data previously reported. The new melting data of β-quartz were combined and optimized with all available thermodynamic, volumetric, and phase equilibria data for β-cristobalite, β-quartz and coesite to produce a P–T liquidus diagram for silica valid up to 6.0 GPa. Using the new optimized thermodynamic parameters, the invariant point β-cristobalite+β-quartz+liquid and β-quartz+coesite+liquid were determined to lie at 1687±17 °C and 0.457 GPa, and 2425±25 °C and 5.00 GPa, respectively.     

Glacier hydrochemistry, solute provenance, and chemical denudation at a surge-type glacier in Kuannersuit Kuussuat, Disko Island, West Greenland

In 1995–1998, Han 11 km terrestrial surge of Kuannersuit Glacier, an outlet glacier of the largest ice cap on Disko Island, West Greenland, affected the catchment dramatically. In order to estimate solute fluxes and provenances, bulk meltwaters were sampled at the main subglacial outlet during the initial part of the quiescent phase. The hydrochemistry is significantly influenced by a subglacial basaltic weathering regime with absence of carbonate minerals. The results show that marine and aerosol derived solutes have minimal contribution to the total ion content, whereas sequestration of atmospheric CO₂ associated with carbonation of Ca-rich feldspar and reactive volcanic glass is more dominant than previously reported from glacierized catchments. Application of a sampling strategy dividing water samples into four groups to determine the content of dissolved HCO₃⁻ and CO₃²⁻ shows that the cationic equivalent weathering rate range is 683–860 Σmeq⁺ m⁻² a⁻¹ and solute flux ranges between 76 and 98 t km⁻² a⁻¹. The crustal denudation rate is estimated to 26 t km⁻² a⁻¹, and the transient CO₂ drawdown amounts to 8500–13700 kg C km⁻² a⁻¹.     

Anelastic structure of the upper mantle beneath the northern Philippine Sea

We investigated the upper mantle anelastic structure beneath the northern Philippine Sea region, including the Izu-Bonin subduction zone and the Shikoku Basin. We used regional waveform data from 69 events in the Pacific and the Philippine Sea slabs, recorded on F-net and J-array network broadband stations in western Japan. Using the S–P phase pair method, we obtained differential attenuation factors, δt^*, which represent the relative whole path Q. We conducted a tomographic inversion using 978 δt^* values to invert for a fine-scale (50–100 km) three-dimensional anelastic structure.

The results shows two high-Q regions (Q_P>1000) which are consistent with the locations of the Pacific and the Philippine Sea slabs. Also there is a low-Q (Q_P110) area extending to the deeper parts (350–400 km) of the model just beneath the old spreading center and the Kinan Seamount Chain in the Shikoku Basin. A small depth dependence of the laterally averaged Q_P was found, with values of 266 (0–250 km), 301 (250–400 km), and 413 (400–500 km).     

Effect of hydrostatic pressure on the lattice parameters of Fe2SiO4 olivine up to 70 kbar

The pressure dependence of the three lattice parameters and unit cell volume of fayalite (Fe₂SiO₄ olivine) was determined by X-ray diffraction under hydrostatic pressures up to 70 kbar. In order to eliminate stress inhomogeneity within a composite material consisting of a specimen mixed with an internal-pressure standard, a liquid (1 : 1 mixture of ethanol and methanol) was used as a pressure-transmitting medium. The isothermal bulk modulus calculated on the basis of the second-order Birch-Murnaghan equation of state gives the values K₀ = 1.19 ± 0.10 Mbar and K₀′ = 7 ± 4, and if we assume K₀′ = 5: K₀ = 1.24 ± 0.02 Mbar. Three axes of fayalite were found to be compressible in the following order, b >c >a. Comparisons with the results obtained under non-hydrostatic compression are made.     

Effect of composition,structure, and spin state on the thermal conductivity of the Earth's lower mantle

The change in electronic structure of iron at high pressures to spin-paired states in ferropericlase, silicate perovskite, and post-perovskite may have a profound influence on the thermal conductivity of the lower mantle. Here, we present optical absorption data for lower mantle minerals to assess the effect of composition (including iron oxidation state), structure, and iron spin state on radiative heat transfer. We confirm that the presence of ferric iron in ferropericlase strongly affects the optical properties, while the effect of the spin-pairing transition may be more secondary. We also show that post-perovskite exhibits larger optical absorption in the near infrared and visible spectral ranges than perovskite which may have a profound effect on the dynamics the lowermost mantle. We present preliminary results from measurements of the phonon thermal conductivity of perovskite at 125 GPa using a pulsed laser heating technique. The available data suggest a larger value than what previously estimated, although the uncertainty is large.     

Prediction of siderophile element metal-silicate partition coefficients to 20 GPa and 2800°C: the effects of pressure, temperature, oxygen fugacity, and silicate and metallic melt compositions

We report new metal-silicate partition coefficients for Ni, Co and P at 7.0 GPa (1650–1750°C), and Ni, Co, Mo, W and P at 0.8, 1.0 and 1.5 GPa (1300–1400°C). Guided by thermodynamics, all available metal-silicate partition coefficients, D(i), where i is Ni, Co, P, Mo and W, are regressed against 1/T, P/T, lnf(O₂), ln(1 − X_s) (X_S is mole fraction of S in metallic liquid) and nbo/t (non-bridging oxygen/tetrahedral cation ratio, a silicate melt compositional-structural parameter) to derive equations of the following form: ln D(i) = aln f(O₂) + (b/T) + (cP/T) + d(nbo/t) + eln(1 − X_S) + f. Expressions for solid metal-liquid silicate and liquid metal-liquid silicate partition coefficients are derived for S-free and S-bearing systems.

We investigate whether Earth's upper-mantle siderophile element abundances can be reconciled with simple metal-silicate equilibrium. Sulfur-free metallic compositions do not allow a good fit. However, Ni, Co, Mo, W and P abundances in the upper mantle are consistent with simple metal-silicate equilibrium at mantle pressures and temperatures (27 GPa, 2200 K, ΔIW(iron-wüstite) = −0.15, nbo/t = 2.7; X_S = 0.15). Although these conditions are near the anhydrous peridotite solidus, they are well above the hydrous solidus and probably closer to the liquidus. A hydrous magma ocean and early mantle are consistent with predicted planetary accretion models. These results suggest that siderophile element abundances in Earth's upper mantle were established by liquid metal-liquid silicate equilibrium near the upper-mantle-lower-mantle boundary.     

Accretion, core formation, H and C evolution of the Earth and Mars

Recent understandings of planetary accretion have suggested that accumulation of a small number of large planetesimals dominates intermediate to final growth stages of the terrestrial planets, with impact velocity high enough to induce extensive melting of the planetesimal and target materials, resulting in formation of a large molten region in which gravitational segregation of silicate and metal, that is, core formation proceeds. In case of homogeneous accretion, volatiles contained in each planetesimal are likely subjected to partitioning among gas, silicate melt, and molten metallic iron at significantly high temperatures and pressures in such a massive molten region. Each phase would subsequently form the proto-atmosphere, -mantle, or-core, respectively. Such chemical reprocessing of H and C associated with core formation, which is followed by both degassing from mantle and atmospheric escape, may result in a diverse range of H₂O/CO₂ in planetary surface environments, which mainly depends on the H and C content relative to metallic iron in planetary building stones. This may explain inferred difference in volatile distribution between the Earth's (relatively H₂O-rich, CO₂-poor) and the martian (H₂O-poor, CO₂-rich) surface environments. Such volatile redistribution may be systematically described by using the retentivity of H₂O, ξ, defined as follows: ξ = 1 − ([CO]⁰ + 2[CH₄]⁰ + 2[C(gr)]⁰)/[H₂O]⁰, where [i]⁰ represents mol number of species i partitioned into non-metallic phases, that is, gas and silicate melt in impact-induced molten region. When ξ > 0.5, relatively H₂O-rich and CO₂-poor surface environment may eventually evolve, although a small portion of H₂O partitioned into the NON=metallic phases are possibly consumed by subsequent chemical reactions with reduced C-species with producing CO₂ and H₂. When ξ< 0.5, on the contrary, H₂O consumption by the above reactions and selective loss of H₂ to space may result in relative H₂O-depleted and CO₂-rich surface environment. Given the building stone composition by the two-component model by Ringwood (1977) and Wänke (1981), ξ is found to decrease with increasing the mixing fraction of the volatile-rich component: ξ > 0.5 for the mixing fraction smaller than about 15–20% and ξ < 0 for the mixing fraction larger than about 20–30%. This is not significantly dependent on temperature and pressure in molten region and H/C ratio in the building stone. The estimated mixing fraction of the volatile-rich component, about 10% for the Earth and 35% for Mars, is consistent with the observed difference in volatile distribution between the surfaces of both planets.     

Mesocosm experiments for evaluating the biological efficacy of ozone treatment of marine ballast water

Ballast water is a major pathway for the transfer of non-indigenous species in aquatic environments. The objectives of this study were to determine the ability of ozone to reduce the numbers of a spectrum of marine organisms collected from Puget Sound, Washington in replicated mesocosm (280 l) experiments, and estimate the minimum ozone concentrations as measured by total residual oxidant (TRO) required to reduce organism densities. Ozone treatment was effective in removing bacteria, phytoplankton, and mesozooplankton with initial TRO concentrations of 2–5 mg l⁻¹ as Br₂. Persistence of TRO resulted in an extended period of toxicity and cumulative mortality. TRO decay allowed bacteria populations to multiply when TRO levels fell below 0.5–1.0 mg l⁻¹ as Br₂. Phytoplankton chlorophyll a concentrations were rapidly reduced by ozone treatment and did not increase in any treatments or controls because of lack of light. Overall mesozooplankton viability was rapidly reduced by 90–99% in treatment TRO levels above 1.85 mg l⁻¹ as Br₂. Our study outlines novel protocols that can be used for testing different potential ballast water treatment systems in replicated and controlled mesocosm experiments.     

A case study on fuel oil contamination in a mangrove swamp in Hong Kong

Mangroves commonly found along tropical and subtropical coastlines are susceptible to oil pollution. In December 2000, around 500 1 m tall Kandelia candel saplings at the age of 3–5 years old located at the foreshore region of Sheung Pak Nai swamp, Hong Kong SAR, were found to be damaged by oil pollution. More than 80% of the saplings were either dead or washed away and leaving less than 5% healthy saplings with dense green leaves. Elevated concentrations of light n-alkanes (ranging from n-C₁₄ to n-C₂₀), pristane and phytane were recorded in surface sediments collected in December 2000. The ratio between light and total n-alkanes was 0.4. The total petroleum hydrocarbons (60–80 μg g⁻¹ TPH) and unresolved complex mixtures (60–70 μg g⁻¹ UCM) were higher than the background values of other mangrove sediments in Hong Kong, which were 40 and 20 μg g⁻¹, respectively. In certain root zone sediments, TPH concentrations were above 1000 μg g⁻¹. These results suggest that surface sediments in Sheung Pak Nai were contaminated by petroleum oil, most likely by illegal discharge of fuel oil which occurred between 1998 and 2002. One year later, in December 2001, unhealthy saplings had recovered and re-grown. The concentrations of TPH and UCM in sediments declined to around 40 μg g⁻¹, pristane and phytane dropped by 80%, and the ratio of light to total n-alkanes was 0.15, suggesting that residual oil in sediments was weathered leading to a remarkable recovery of the unhealthy saplings.