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.     

Helium isotope geochemistry of some volcanic rocks from Saint Helena

³He/⁴He ratios have been measured for olivine and clinopyroxene phenocrysts in 7–15 m.y. old basaltic lavas from the island of St. Helena. Magmatic helium was effectively resolved from post-eruptive radiogenic helium by employing various extraction techniques, includingin vacuo crushing, and stepwise heating or fusion of the powders following crushing. The inherited³He/⁴He ratio at St. Helena is 4.3–5.9 R_A. Helium isotope disequilibrium is present within the phenocrysts, with lower³He/⁴He upon heating and fusion of the powders following crushing, due to radiogenic ingrowth or to -particle implantation from the surrounding(U + Th)-rich lavas.

A single crushing analysis for clinopyroxene in a basalt from Tubuaii gave³He/⁴He= 7.1 R_A.³He/⁴He ratios at St. Helena and Tubuaii (HIMU hotspots characterized by radiogenic Pb isotope signatures) are similar to³He/⁴He ratios previously measured at Tristan da Cunha and Gough Island (EM hotspots characterized by low²⁰⁶Pb/²⁰⁴Pb). Overall, the HeSrPb isotope systematics at these islands are consistent with a mantle origin as contiguous, heterogeneous materials, such as recycled crust and/or lithosphere.³He/⁴He ratios at HIMU hotspots are similar to mantle xenoliths which display nearly the entire range of Pb isotope compositions found at ocean islands, and are only slightly less than values found in mid-ocean ridge basalts (7–9 R_A). This suggests that the recycled materials were injected into the mantle within the last 10⁹ yrs.     

How chalcophile is rhenium? An experimental study of the solubility of Re in sulphide mattes

Although the Re/Os isotopic system has proved to be a valuable aid in understanding the evolution of the Earth's mantle, interpretation of the data is currently hindered by limited knowledge of the high-temperature geochemical behaviour of Re. In particular, the extent to which Re in the mantle is hosted by sulphide or silicate phases is poorly known. We report the results of an experimental study of the solubility of Re in sulphide melts (called here “mattes”) coexisting with a Re-rich Re–Fe alloy in the system Fe–Re–S–O over a range of fO₂, fS₂ and temperatures, which allow extrapolation to conditions pertinent to the Earth's mantle. The solubility of Re in mattes increases with increasing fS₂, with Re dissolving as Re⁴⁺ at high fS₂ and Re⁰ at low fS₂. The effect of fO₂ is negligible except at high fO₂ where O in the matte becomes important. At constant fS₂, an increase in temperature leads to an increase in the solubility of Re⁰ in the matte, but a decrease in the solubility of Re⁴⁺. These results, coupled with data for the Re solubility in silicate melts taken from the literature, allow the calculation of Re matte/silicate–melt partition coefficients (D_Re^matte/sil) for a range of conditions. The calculated D_Re^matte/sil show a large dependence on fO₂, and a lesser dependency on fS₂, with Re behaving as a chalcophile element for relatively reduced MORB-type mantle and as a lithophile element for the oxidised sources of island-arc basalts. The sensitivity of Re to fS₂ and fO₂ reconciles the apparent discrepancies between previous estimates of this parameter, which can vary by more than five orders of magnitude within the range of fS₂ and fO₂ covered by terrestrial basaltic magmas.     

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO₂CO fluids in a mid-ocean ridge basalt (morb) has been measured at 1200°C, 500–1500 bar, and oxygen fugacities between NNO and NNO-4. High oxygen fugacities, and thus CO₂-rich fluids, were produced by using a starting material equilibrated at NNO, and Ag₂C₂O₄ as the fluid source. Low oxygen fugacities were achieved by using graphite capsules, and MgCO₃ as the fluid source. These graphite-saturated fluids have the lowest possibleC/O₂CO ratio for a given pressure and temperature.

Experiments were run in a rapid-quench internally heated pressure vessel. Fluid compositions were measured using a simple vacuum technique and by Raman spectroscopy of fluid inclusions. The two techniques yielded comparable results. Fourier transform micro-infrared spectroscopy was used to identify and measure concentrations of dissolved volatiles in double-polished wafers of the quenched glasses. Carbonate was the only carbon-bearing species identified. Raman spectroscopic analysis of inclusion-free areas of glass confirmed the absence of dissolved molecular CO₂, CO and carbon. The measured concentrations of dissolved CO₂ in the glasses were proportional to the fugacity of CO₂ during the experiments, calculated from the measured fluid compositions. The data were fit to the equationX_CO2^melt(ppm)= 0.492 fCO₂ (bar).

The insolubility of CO, compared to CO₂, may be related to the fact that dissolution of CO requires reduction of another species in the melt, whereas dissolution of CO₂ does not. Due to the fact that CO will be an important component of natural CO fluids at low pressures and low oxygen fugacities, equilibrium dissolved CO₂ contents will be less than calculated assuming pure CO₂ fluids, but as theC/O₂CO ratio in a pure CO fluid at fixed pressure and temperature is a direct function of oxygen fugacity, measurement of the oxygen fugacity of quenched glasses or trapped fluids in natural samples should allow saturation concentrations to be calculated. Dissolved CO₂ contents of somemorb are less than expected if they were in equilibrium with pure CO₂. These samples must, therefore, have been more reduced than average if they were fluid-saturated. Together with results from other studies of CO₂ and H₂O solubilities in basalt, the results of this study provide a comprehensive framework for modelling CO₂ solution inmorb.     

Trace element and Sr and Nd isotope geochemistry of peridotite xenoliths from the Eifel (West Germany) and their bearing on the evolution of the subcontinental lithosphere

Peridotite xenoliths from the Eifel can be divided into incompatible element-depleted and -enriched members. The depleted group is restricted to dry lherzolites whereas the enriched group encompasses dry harzburgites, dry websterite and amphibole and/or phlogopite-bearing peridotites. Isotopically the depleted group is very diverse with¹⁴³Nd/¹⁴⁴Nd ranging from 0.51302 to 0.51355 and⁸⁷Sr/⁸⁶Sr from 0.7041 to 0.7019, thus occupying a field larger than expected for oceanic-type subcontinental mantle. These xenoliths are derived from a mantle which appears to have diverged from a bulk-earth Nd and Sr isotopic evolution path 2 Ga ago as a consequence of partial melting. The combination of high¹⁴³Nd/¹⁴⁴Nd with high⁸⁷Sr/⁸⁶Sr in some members of the depleted-xenoliths suite is likely to be the result of incipient reaction with incompatible element-enriched fluids in the mantle. In the enriched group such reactions have proceeded further and erased any pre-enrichment isotope memory resulting in a smaller isotopic diversity (¹⁴³Nd/¹⁴⁴Nd 0.51256–0.51273,⁸⁷Sr/⁸⁶Sr 0.7044–0.7032). An evaluation of SmHf and YbHf relationships suggests that the amphibole-bearing lherzolites and harzburgites acquired their high enrichment of light rare earth elements by fluid infiltration into previously depleted peridotite rather than by silicate melt-induced metasomatism. Upper mantle composed of such metasomatized peridotites does not represent a potential source for the basanites and nephelinites from the Eifel. The isotopic and chemical diversity of the subcontinental lithospheric part of the mantle may result from it having remained isolated from the convecting mantle for times > 1 Ga.     

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.     

Geodynamic significance of ultramafic xenoliths from Eastern Serbia: Relics of sub-arc oceanic mantle?

A suite of highly depleted peridotite xenoliths in East Serbian Palaeogene basanites represents the lithospheric mantle beneath the Balkan Peninsula. The xenoliths are harzburgites, clinopyroxene-poor lherzolites and rare dunites. They contain mostly <5 vol.% of modal clinopyroxene and are characterized by high Mg# in silicates (>91), high Cr# in spinel (mostly 0.5–0.7), and by distinctively low Al₂O₃ contents in orthopyroxene (mostly 1–2 wt.%). They have experienced some mantle metasomatism which has slightly obscured their original composition. Nevertheless, the general characteristics of the xenoliths imply a composition which is significantly more depleted than most non-cratonic sub-continental mantle xenolith suites, as well as orogenic peridotites and abyssal peridotites. Geological and compositional evidence suggests that the xenoliths do not represent Archean mantle. The existence of Proterozoic mantle cannot be entirely excluded, although it is in disagreement with geological evidence. On the other hand, the studied xenoliths are compositionally very similar to peridotites of modern oceanic sub-arc settings. The existence of such a depleted lithospheric mantle segment is also inferred from the presence of rare orthopyroxene-rich xenoliths in the same suite. These are interpreted to have originated as lithospheric precipitates of high-Mg, SiO₂-saturated magmas that require a highly depleted mantle source. Such source is typically required by boninitic-like magmas of intraoceanic suprasubduction settings. A proposed geodynamic model to explain these observations involves accretion or underplating of the lower parts of the Tethyan oceanic lithosphere during the Upper Jurassic closure of the eastern branch of the Vardar ocean.     

Geothermal gradient of the upper mantle beneath Jeju Island, Korea: Evidence from mantle xenoliths

Abstract Ultramafic xenoliths found in alkali basalts from Jeju Island, Korea are mostly spinel lherzolites accompanied by subordinate amount of spinel harzburgites and pyroxenites. The combination of results from a two-pyroxene geothermometer and Ca-in-olivine geobarometer yields temperature–pressure (T–P) estimates for spinel peridotites that fall in experimentally determined spinel lherzolite field in CaO-Fe-MgO-Al₂O₃-SiO₂-Cr₂O₃ (CFMASCr) system. These T–P data sets have been used to construct the Quaternary Jeju Island geotherm, which defines a locus from about 13 kbar at 880°C to 26 kbar at 1040°C. The geothermal gradient of Jeju Island is greater than that of the conventional conductive models, and may be as a result of a thermal perturbation by the heat input into the lithospheric mantle via the passage and emplacement of magma. Spinel–lherzolite is the main constituent rock-type of the lithospheric mantle beneath Jeju Island. Pyroxenites may be intercalated in peridotites at similar depth and temperature as re-equilibrated veins or lenses.     

Characteristics of subcontinental lithospheric mantle beneath Baegryeong Island, Korea: Spinel peridotite xenoliths

Abstract   Geochemical data on Baegryeong Island spinel peridotites found in Miocene alkali basalt provide the information for lithosphere composition, chemical processes, equilibrium pressure and temperature conditions. Spinel peridotite xenoliths, showing transitional textures between protogranular and porpyroclastic textures, were accidentally trapped by the ascending alkali basalt magma. The xenoliths originate at depths from 50 to 70 km with a temperature range from 800 to 1100°C. The variations of modal and mineral compositions of the spinel peridotite xenoliths indicate that the xenoliths have undergone 1–10% fractional melting. The spinel peridotites from Baegryeong Island have undergone cryptic mantle metasomatism subsequent to melt extraction. Metasomatic agent of enriched spinel peridotite xenoliths was carbonatite melt.     

A model for the layered upper mantle

Numerical modeling of mantle convection by Liu (1994, Science, 264: 1904–1907) favors a two-layer convection, if the results are reinterpreted for the correct phase relations in (Mg,Fe)₂SiO₄. The resulting chemical isolation of the upper and lower mantle suggests a highly differentiated and layered upper mantle to account for the discrepancy between the observed compositions of mantle xenoliths and the cosmic abundances of elements. It is shown that a layered upper mantle with a hidden reservoir can have a structure consistent with the observed seismic velocity profiles and an average bulk composition corresponding to the cosmic abundances. The evolution of the upper mantle and the origin of komatiites are discussed in the context of the proposed model.     

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 water contents in pyroxenes from spinel-peridotites of the oxidized, sub-arc mantle wedge

Pyroxene water contents measured by Fourier transform infrared spectrometry for Mexican and Simcoe (WA, USA) spinel-peridotite xenoliths range from 140 to 528 ppm in clinopyroxenes and 39 to 265 ppm in orthopyroxenes. Correlations between these water contents and major-element compositional data for the pyroxenes, associated spinels, and whole-rock xenoliths demonstrate that these water contents record mantle values that have not been perturbed since the xenoliths were brought to the surface by their host magmas. Broad positive correlations of pyroxene water contents with whole-rock Al₂O₃ are consistent with water behaving as an incompatible element during peridotite melting. The main control on the range of pyroxene water contents, however, appears to be the redox state of the peridotite, because estimates of oxygen fugacity from Mössbauer (Simcoe) and microprobe data (Mexico) on spinels are negatively correlated with water contents. This is consistent with the dominant mechanism of H incorporation into pyroxene, which is dependent on the oxidation-reduction of iron. Metasomatism of sub-arc mantle-wedge peridotites by oxidized fluids or melts rising from the slab raises the oxygen fugacity of the peridotites, and where temperature is high enough, induces them to partially melt. The oxidation, in turn, lowers the solubility of water in the peridotite minerals, causing more than half of the original water to be expelled. That water enters the hydrous partial melts and these ascend through the lithosphere to feed the arc magmatic system in the upper crust. Low water contents in pyroxenes from sub-arc mantle-wedge peridotites, such as those from Simcoe and some western Mexican sites, therefore appear to be complementary to the high water contents that characterize subduction-zone magmas and fuel their explosive eruptions. An estimate of water budget in subduction zones, however, indicates that the amount of water coming from the dehydration of mantle-wedge anhydrous minerals probably accounts for less than 5% of the total water present in subduction-related magmas. The high water contents of arc magmas thus are mainly attributed to fluids or melts from the slab proper. The relatively dry sub-arc mantle wedge appears to be an effective medium through which subducted water is transported from slabs toward the surface.     

Origin of fine‐grained peridotite xenoliths from Iraya volcano of Batan Island,Philippines: deserpentinization or metasomatism at the wedge mantle beneath an incipient arc?

Abstract Peridotite xenoliths from the subarc mantle, which have been rarely documented, are described from Iraya volcano of the Luzon arc, the Philippines, and are discussed in the context of wedge-mantle processes. They are mainly harzburgite, with subordinate dunite, and show various textures from weakly porphyroclastic (C-type) to extremely fine-grained equigranular (F-type). Textural characteristics indicate a transition from the former to the latter by recrystallization. The F-type peridotite has inclusion-rich fine-grained olivine and radially aggregated orthopyroxene, being quite different in texture from ordinary mantle-derived peridotites previously documented. Despite their strong textural contrast, the two types do not show any systematic difference in modal composition. The harzburgite of C-type has ordinary mantle peridotite mineralogy; olivine is mostly Fo91–92 and chromian spinel mostly has Cr#s (= Cr/[Cr + Al] atomic ratios) from 0.3 to 0.6. Olivine is slightly more Fe-rich (Fo89–91) and spinel is more enriched in Cr (the Cr#, 0.4–0.8) and Fe³⁺ in F-type peridotites than in C-type harzburgite. Orthopyroxene in F-type peridotites is relatively low in CaO (<1 wt%), Al₂O₃ (<2 wt%) and Cr₂O₃ (<0.4 wt%). The F-type peridotite was possibly formed from the C-type one by recrystallization including local dissolution and precipitation of orthopyroxene assisted by fluid (or melt) of subduction origin. Textural characteristics, however, indicate a deserpentinization origin from abyssal serpentinite of which protolith was a C-type peridotite. In this scenario the initial abyssal serpentinite was possibly dehydrated due to an initiation of magmatic activity beneath an incipient oceanic arc like Batan Island. The F-type peridotite is characteristic of the upper mantle of island arc, especially of incipient arc.     

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.     

Intermittent exposure to reduced oxygen levels affects prey size selection and consumption in swimming crab Thalamita danae Stimpson

Portunid crabs Thalamita danae (carapace width: 46–56 mm) were exposed to low oxygen level (4.0 mg O₂ l⁻¹) and hypoxia (1.5 mg O₂ l⁻¹) for 6 h each day with three size classes (large: 15.0–19.9 mm, medium: 10.0–14.9 mm, small: 5.0–9.9 mm) of mussels Brachidontes variabilis offered as food. Consumption rate, prey size preference, and prey handling including breaking time, handling time, eating time and prey value, were studied during the time the crabs were exposed to reduced oxygen levels and results were compared with the crabs maintained at high oxygen level (8.0 mg O₂ l⁻¹) throughout the experiment. Consumption of mussels from all size classes was significantly higher at high oxygen level than at reduced oxygen levels. No mussel size preference was observed for crabs exposed to 4.0 or 8.0 mg O₂ l⁻¹ but those crabs exposed to 1.5 mg O₂ l⁻¹ preferred medium mussels. Both breaking time and handling time increased with mussel size but did not vary with oxygen level. Prey value of each mussel consumed (mg dry wt eaten crab⁻¹ s⁻¹) was calculated by dividing the estimated dry weight of the mussel by the observed handling time. Mean prey value varied significantly with mussel size, with values obtained for large mussels being higher than small mussels at 4.0 and 8.0 mg O₂ l⁻¹; the effect of oxygen level, however, was insignificant. In view of portunid crabs as major predators of mussels, results may help explain dominance of mussels in eutrophic harbours in Hong Kong.     

Helium isotope geochemistry of mid-ocean ridge basalts from the South Atlantic

We report new helium isotope results for 49 basalt glass samples from the Mid-Atlantic Ridge between 1°N and 47°S.³He/⁴He in South Atlantic mid-ocean ridge basalts (MORB) varies between 6.5 and 9.0 R_A (R_A is the atmospheric ratio of1.39 × 10⁻⁶), encompassing the range of previously reported values for MORB erupted away from high³He/⁴He hotspots such as Iceland. He, Sr and Pb isotopes show systematic relationships along the ridge axis. The ridge axis is segmented with respect to geochemical variations, and local spike-like anomalies in³He/⁴He, Pb and Sr isotopes, and trace element ratios such as(La/Sm)_N are prevalent at the latitudes of the islands of St. Helena, Tristan da Cunha and Gough to the east of the ridge. The isotope systematics are consistent with injection beneath the ridge of mantle “blobs” enriched in radiogenic He, Pb and Sr, derived from off-axis hotspot sources. The variability in³He/⁴He along the ridge can be used to refine the hotspot source-migrating-ridge sink model.

MORB from the 2–7°S segment are systematically the least radiogenic samples found along the mid-ocean ridge system to date. Here the depleted mantle source is characterized by⁸⁷Sr/⁸⁶Sr of 0.7022, Pb isotopes close to the geochron and with²⁰⁶Pb/²⁰⁴Pb of 17.7, and³He/⁴He of 8.6–8.9 R_A. The “background contamination” of the subridge mantle, by radiogenic helium derived from off-ridge hotspots, displays a maximum between 20 and 24°S. The HePb and HeSr isotope relations along the ridge indicate that the³He/⁴He ratios are lower for the hotspot sources of St. Helena, Tristan da Cunha and Gough than for the MORB source, consistent with direct measurements of³He/⁴He ratios in the island lavas. Details of the HeSrPb isotope systematics between 12 and 22°S are consistent with early, widespread dispersion of the St. Helena plume into the asthenosphere, probably during flattening of the plume head beneath the thick lithosphere prior to continental breakup. The geographical variation in theHe/Pbratio deduced from the isotope systematics suggests only minor degassing of the plume during this stage. Subsequently, it appears that the plume component reaching the mid-Atlantic ridge was partially outgassed of He during off-ridge hotspot volcanism and related melting activity.

Overall, the similar behavior of He and Pb isotopes along the ridge indicates that the respective mantle sources have evolved under conditions which produced related He and Pb isotope variations.     

Enrichment of the continental lithosphere by OIB melts: Isotopic evidence from the volcanic province of northern Tanzania

Alkali basalts and nephelinites from the southern end of the East African Rift (EAR) in northern Tanzania have incompatible trace element compositions that are similar to those of ocean island basalts (OIB). They define a considerable range of Sr, Nd and Pb isotopic compositions (⁸⁷Sr/⁸⁶Sr= 0.7035−0.7058,ε_Nd = −5to+3, and²⁰⁶Pb/²⁰⁴Pb= 17.5−21.3), each of which partially overlaps the range found in OIB. However, they occupy a unique position in combined Nd, Sr and Pb isotopic compositional space. Nearly all of the lavas have radiogenic Pb, similar to HIMU with high time-integrated²³⁸U/²⁰⁴Pb coupled with unradiogenic Nd (+2 to −5) and radiogenic Sr (>0.704), similar to EMI. This combination has not been observed in OIB and provides evidence that these magmas predominantly acquired their Sr, Nd and Pb in the subcontinental lithospheric mantle rather than in the convecting asthenosphere. These data contrast with compositions for lavas from farther north in the EAR. The Pb isotopic compositions of basalts along the EAR are increasingly radiogenic from north to south, indicating a fundamental change to sources with higher time-integratedU/Pb, closer to the older cratons in the south. An ancient underplated OIB melt component, isolated for about 2 Ga as enriched lithospheric mantle and then remelted, could generate both the trace element and isotopic data measured in the Tanzanian samples. Whereas the radiogenic Pb in Tanzanian lavas requires a source with high time-integratedU/Pb, most continental basalts that are thought to have interacted with the continental lithospheric mantle have unradiogenic Pb, requiring a source with a history of lowU/Pb. Such lowU/Pb is readily accomplished with the addition of subduction-derived components, since the lower averageU/Pb of arc basalts (0.15) relative to OIB (0.36) probably reflects addition of Pb from subducted oceanic crust. If the subcontinental lithosphere is normally characterized by low time-integratedU/Pb it would appear that subduction magmatism is more important than OIB additions in supplying the Pb inventory of the lithospheric mantle. However,U/Pb ratios of xenoliths derived from the continental lithospheric mantle suggest that both processes may be important. This apparent discrepancy could be because xenoliths are not volumetrically representative of the subcontinental lithospheric mantle, or, more likely, that continental lithospheric mantle components in basalts are normally only identified as such when the isotopic ratios are dissimilar from MORB or OIB. Lithospheric enrichment from subaccreted OIB components appears to be more significant than generally recognized.     

Water contents of clinopyroxenes from sub‐arc mantle peridotites

One poorly constrained reservoir of the Earth's water budget is that of clinopyroxene in metasomatised, mantle peridotites. This study presents reconnaissance Sensitive High‐Resolution, Ion Microprobe–Stable Isotope (SHRIMP–SI) determinations of the H₂O contents of (dominantly) clinopyroxenes in rare mantle xenoliths from four different subduction zones, i.e. Mexico, Kamchatka, Philippines, and New Britain (Tabar‐Feni island chain) as well as one intra‐plate setting (western Victoria). All of the sub‐arc xenoliths have been metasomatised and carry strong arc trace element signatures. Average measured H₂O contents of the pyroxenes range from 70 ppm to 510 ppm whereas calculated bulk H₂O contents range from 88 ppm to 3 737 ppm if the variable presence of amphibole is taken into account. In contrast, the intra‐plate, continental mantle xenolith from western Victoria has higher water contents (3 447 ppm) but was metasomatised by alkali and/or carbonatitic melts and does not carry a subduction‐related signature. Material similar to the sub‐arc peridotites can either be accreted to the base of the lithosphere or potentially be transported by convection deeper into the mantle where it will lose water due to amphibole breakdown.     

On the strength of electric currents and zonal magnetic fields at the top of the Earth''s core: Methodology and preliminary estimates

A new method is described for estimating: (a) the meridional electric current density, j_θ, (b) the vertical growth rate of the zonal magnetic field, ∂B_φ/∂r, or its scale-height, B_φ/∂B_φ/∂r) and (c) the vertical growth rate of the vertical current density, ∂j_r/∂r, at a few isolated points on the top surface of the Earth's core from observations of the internal geomagnetic field at the Earth's surface. The theoretical technique rests on combining unaccelerated, gravitationally-driven Boussinesq fluid dynamics of the core with frozen-flux electromagnetism, the mantle being treated as a spherically symmetric insulator.

Insertion into this theory of main field models for epochs 1965, 1975 leads to preliminary values for these quantities of magnitude: (a) j_θ 1 A/m², (b) ∂B_φ/∂r 10⁻⁶ T/m or B_φ/(∂B_φ/∂r) 10 m, (c) ∂j_r/∂r 10⁻⁶ A/m³. Some geophysical implications of these estimates are discussed.     

CRYSTALLOGRAPHIC PREFERRED ORIENTATION(CPO) OF ANISOTROPIC MINERALS IN THE LITHOSPHERE AND ITS SIGNIFICANCE TO THE STUDY OFLITHOSPHERE DYNAMICS

Seismic anisotropy has been widely used to constrain deformation and mantle flow within the upper mantle of the Earth's interior, and is mainly affected by crystallographic preferred orientation(CPO)of anisotropic mineral in lithosphere. Anisotropy of peridotites caused by deformation is the main source of seismic anisotropy in the upper mantle. Olivine is the most abundant and easily deformed mineral to form CPO in peridotite, thus the CPO of olivine controls seismic anisotropy in the upper mantle. Based on simple shear experiments and studies of natural peridotites deformation, several CPO types of olivine have been identified, including A, B, C, D, E and AG-type. Studies on the deformation of olivine have shown that the CPO of olivine is mainly related to stress, water content, temperature, pressure, partial melting and melt/fluid percolation. Most of the seismic anisotropy has been explained by the A-type olivine CPO in the upper mantle, which is commonly found in upper-mantle peridotites and produced by the simple shear in dry conditions. Previous studies showed that anisotropy was attributed to the CPO of mica and amphibole in the middle-lower crust. The comparison between mantle anisotropy calculated from mineral CPO and regional anisotropy deduced from geophysical methods is therefore particularly useful for interpreting the deformation mechanisms and geodynamic processes which affect the upper mantle in different tectonic units such as subduction system, continental rift and continental collision zone in the world. The paper summarizes the characteristics of CPO and anisotropy of major anisotropic minerals in the upper mantle. Taking the lithosphere mantle xenoliths in the southeastern Tibetan plateau as an example, we perform detailed studies on the microstructures and seismic anisotropy to better understand the deformation mechanisms and upper mantle anisotropy in this region. Results show that the CPO of olivine in peridotite xenoliths in southeastern Tibetan plateau are A-type and AG-type. The mechanisms proposed for the formation of AG-type are different from that for the A-type. Therefore, the occurrence of AG-type olivine CPO pattern suggests that this CPO may record a change in deformation mechanism and tectonic environment of the lithosphere in southeastern Tibetan plateau. Provided that the strong SKS(shear wave splitting)observed in southeastern Tibetan plateau results from lithosphere mantle, the lithosphere mantle in this region is expected to be at least 130km thick and characterized by vertical foliation. Considering that the thickness of lithosphere in southeastern Tibetan plateau is much less than 130km and the lithosphere mantle cannot explain the anisotropy measured by SKS, other anisotropy sources should be considered, such as anisotropy in the asthenosphere and the oriented melt pockets(MPO)in the upper mantle. Therefore, detailed study of CPO of anisotropic mineral is essential for constraining geophysical measurements and analyzing the dynamic process of the lithosphere reasonably.