Apatite/liquid partition coefficients for the rare earth elements and strontium

Sixteen sets of apatite/liquid partition coefficients (D^ap/liq) for the rare earth elements (REE; La, Sm, Dy, Lu) and six values for Sr were experimentally determined in natural systems ranging from basanite to granite. The apatite + melt (glass) assemblages were obtained from starting glasses artificially enriched in REE, Sr and fluorapatite components; these were run under dry and hydrous conditions of 7.5–20 kbar and 950–1120°C in a solid-media, piston-cylinder apparatus. An SEM-equipped electron microprobe was used for subsequent measurement of REE and Sr concentrations in coexisting apatites and quenched glasses. The resulting partition coefficient patterns resemble previously determined apatite phenocryst/groundmass concentration ratios in the following respects: (1) the rare earth patterns are uniformly concave downward (i.e., the middle REE are more compatible in apatite than the light and heavy REE); (2) D_REE^ap/liq is much higher for silicic melts than for basic ones; and (3) strontium (and therefore Eu²⁺) is less concentrated by apatite than are the trivalent REE. The effects of both temperature and melt composition on D_REE^ap/liq are systematic and pronounced. At 950°C, for example, a change in melt SiO₂ content from 50 to 68 wt.% causes the average REE partition coefficient to increase from ～7 to ～30. A 130°C increase in temperature, on the other hand, results in a two-fold decrease in D_REE^ap/liq. Partitioning of Sr is insenstitive to changes in melt composition and temperature, and neither the Sr nor the REE partition coefficients appear to be affected by variations in pressure or H₂O content of the melt.The experimentally determined partition coefficients can be used not only in trace element modelling, but also to distinguish apatite phenocrysts from xenocrysts in rocks. Reported apatite megacryst/host basalt REE concentration ratios [12], for example, are considerably higher than the equilibrium partition coefficients, which suggest that in this particular case the apatite is actually xenocrystic.A reversal experiment incorporated in our study yielded diffusion profiles of REE in apatite, from which we extracted a REEαCa interdiffusion coefficient of 2–4×10^?14 cm²/s at 1120°C. Extrapolated downward to crustal temperatures, this low value suggests that complete REE equilibrium between felsic partial melts and residual apatite is rarely established.     

Dynamical geochemistry of the Hawaiian plume

This paper presents a simple dynamical model for melting and trace element distribution in the Hawaiian mantle plume. I model the plume as a partially molten stagnation point flow against the oceanic lithosphere, and obtain solutions for the temperature, melt migration rate, and trace element concentration within it. Trace element concentrations in the melt exceed simple batch melting predictions by up to 70%. The magnitude of this effect depends strongly on the solid-melt partition coefficientK. Trace elements with differentK therefore experience a “dynamical fractionation” within the plume, and incompatible trace element ratios such asLa/Ce always exceed the batch melting predictions. I suggest a simple model for plume-lithosphere interaction in which melts from these two sources mix in proportions determined by thermodynamic constraints. The model can explain the composition of basalts from Haleakala if the degree of melting of the lithosphereF₁ decreases with time from roughly 10% for tholeiites to 2% for alkalic basalts. These values are considerably higher than previous estimates ofF₁ < 1%, and imply correspondingly smaller and more realistic values ( 10 km) for the thickness of the melted part of the lithosphere. Partial melting of additional depleted sources such as the asthenosphere is therefore not required by the Haleakala data. Estimates ofF₁ are highly sensitive to the values chosen for the partition coefficients, however, and should therefore be interpreted with caution.     

Lithium tracer-diffusion in an alkali-basaltic melt — An ion-microprobe determination

An ion-microprobe-based technique has been used to measure lithium tracer-diffusion coefficients (D_Li) in an alkali-basaltic melt at 1300, 1350 and 1400°C. The results can be expressed in the form:D_Li=7.5 ×10^?2exp(?27,600/RT)cm²S^?1The results show significantly faster diffusion rates than those previously recorded for other monovalent, divalent and trivalent cations in a tholeiitic melt. Consequently, diffusive transport of ions acting over a given time in a basaltic melt can produce a wider range of transport distance values than hitherto supposed. Hence, it is concluded that great care should be exercised when applying diffusion data to petrological problems.     

Viscosity and structural changes of albite (NaAlSi3O8) melt at high pressures

Viscosity of anhydrous albite melt, determined by the falling-sphere method in the solid-media, piston-cylinder apparatus, decreases with increasing pressure from 1.13 × 10⁵ P at 1 atm to 1.8 × 10⁴ P at 20 kbar at 1400°C. The rate of decrease in viscosity is larger between 12 and 15 kbar than in other pressure ranges examined. The density of the quenched albite melt increases with increasing pressure of quenching from 2.38 g/cm³ at 1 atm to 2.53 g/cm³ at 20 kbar. The rate of increase in density is largest at pressures between 15 and 20 kbar. The melting curve of albite shows an inflexion at about 16 kbar. These observations strongly suggest that structural changes of albite melt would take place effectively at pressures near 15 kbar. Melt of jadeite (NaAlSi₂O₆) composition shows very similar changes in viscosity and density and a melting curve inflexion at pressures near 10 kbar. Difference in pressure for the suggested effective structural changes of albite and jadeite melts is 5–6 kbar, which is nearly the same as that between the subsolidus reaction curves nepheline + albite= 2jadeite and albite=jadeite + quartz. The structural changes of the melts are, however, continuous and begin to take place at pressures lower than those of the crystalline phases.     

143Nd/144Nd,87Sr/86Sr and trace element constraints on the petrogenesis of Aleutian island arc magmas

¹⁴³Nd/¹⁴⁴Nd,⁸⁷Sr/⁸⁶Sr and trace element results are reported for volcanic and plutonic rocks of the Aleutian island arc. The Nd and Sr isotopic compositions plot within the mantle array with ε_Nd values of from 6.5 to 9.1 and⁸⁷Sr/⁸⁶Sr ratios of from 0.70289 to 0.70342. Basalts have mildly enriched light REE abundances but essentially unfractionated heavy REE abundances, while andesites exhibit a greater degree of light to heavy REE fractionation. Both the basalts and andesites have significant large ion lithophile element to light rare earth element (LILE/LREE) enrichments. Variations in the isotopic compositions of Nd and Sr are not related to the spatial distribution of volcanoes in the arc, nor are they related to temporal differences. ε_Nd and⁸⁷Sr/⁸⁶Sr do not correlate with major element compositions but do, however, correlate with certain LILE/LREE ratios (e.g. Ba_N/La_N). Plutonic rocks have isotropic and trace element characteristics identical to some of the volcanic rocks. Rocks that make up the tholeiitic, calc-alkaline and alkaline series in the Aleutians do not come from isotopically distinct sources, but do exhibit some differing LILE characteristics.Given these elemental and isotopic constraints it is shown that the Aleutian arc magmas could not have been derived directly from homogeneous MORB-type mantle, or fresh or altered MORB subducted beneath the arc. Mixtures of partially altered MORB with deep-sea sediment can in principle account for the isotopic characteristics and most of the observed LILE/LREE enrichments. However, some samples have exceedingly high LILE/LREE enrichments which cannot be accounted for by sediment contamination alone. For these samples a more complex scenario is considered whereby dehydration and partial melting of the subducted slab, containing less than 8% sediment, produces a LILE-enriched (relative to REE) metasomatic fluid which interacts with the overlying depleted mantle wedge. The isotopic and LILE characteristics of the mantle are extremely sensitive to metasomatism by small percentages of added fluid, whereas major elements are not substantially effected, Major element compositions of Aleutian magmas are dominantly controlled by the partial melting of this mantle and subsequent crystal fractionation; whereas isotopic and LILE characteristics are determined by localized mantle heterogeneities.     

High-pressure reconnaissance investigation in the system Mg3Al2Si3O12-Fe3Al2Si3O12

Two synthetic end-members and two natural solid solutions of the system Mg₃Al₂Si₃O₁₂-Fe₃Al₂Si₃O₁₂ have been found to display successive phase transformations at increasingly high pressures when they were compressed in a diamond-anvil cell and heated with a YAG laser to temperatures of approximately 1400–1800°C. X-ray diffraction studies of the quenched samples show that the iron-rich garnets apparently first transform to a garnet-related high-pressure phase, then disproportionate into a mixture of magnesiowüstite plus an unknown phase(s). The latter phase(s) may further transform to a still denser unknown phase(s). The ultimate high-pressure phase may be a perovskite-like structure as was previously found for the magnesium-rich garnets. One of the unknown phases may be the high-pressure phase of Al₂O₃ · nSiO₂ compounds. Magnesium-rich garnets display similar phase transformations as do the iron-rich garnets with the exception of the garnet-related high-pressure phase. These results disagree with a previous interpretation for the high-pressure phase of iron-silicate garnets recovered in shock-wave experiments reported by Ahrens and Graham (1972).     

Co2+ as a chemical analogue for Fe2+ in high-temperature experiments in basaltic systems

High-temperature experiments on ferromagnesian compositions have been hampered by the rapid absorption of up to 95% of the original iron by platinum and 40% by silver-palladium capsules. Molybdenum or iron capsule materials can decrease or alleviate iron loss, but restrict oxygen fugacities to values near the iron-wustite buffer. Because Co²⁺ is stable at f_O2 =HM and because the solubility of Co in platinum in this range of f_O2 is ～0.05% at temperatures to 1350°C, its use as an analogue for Fe²⁺ is possible. In addition, experiments simulating various Fe²⁺ ratios can be easily performed by choosing appropriate Co²⁺/Fe³⁺ ratios. The cobalt phases produced possess brilliant and distinctive colors which are valuable aids in optical identification of minute phases. The cobalt analogue hypothesis was tested with atmospheric pressure experiments in air on the cobalt analogue of the 1921 Kilauea basalt at three simulated Fe²⁺/Fe³⁺ ratios. The results were compared with those of R.E.T. Hill (1969) for the natural 1921 basalt. The phase relations were the same, with the cobalt system stability fields systematically shifted by about +50°C. Microprobe analysis of olivines and the coexisting glasses indicate that the distribution of Co²⁺ between olivine and melt is independent of temperature and liquid composition. Although the analogue liquid composition differs from the equilibrium composition of the natural system, it may be corrected be employing distribution coefficients (K_D = 0.61 for the Co system; K_D = 0.33 for the Fe system) to closely approximate what the natural system would yield if iron loss did not occur.     

Spinel disproportionation at high pressure: calorimetric determination of enthalpy of formation of Mg2SnO4 and Co2SnO4 and some implications for silicates

The enthalpies of formation from the oxides of Mg₂SnO₄ and Co₂SnO₄ were found by oxide melt solution calorimetry to be +1.13 ± 0.48 kcal/mol and ?2.31 ± 0.28 kcal/mol, respectively. Using these data, the slopes, ?P/?T, for disproportionation of these spinels to the component oxides at high pressure were calculated to be +30.4 ± 4.2 bar/K for Mg₂SnO₄ and ?10.3 ± 2.4 bar/K for Co₂SnO₄, in general agreement with the data of Jackson et al. (1974a,b). Using thermochemical data for the formation of olivines, for olivine-spinel transitions and for the transformation of quartz to stishovite, we calculate pressures for the disproportionation of silicate spinels to be in the range 150–200 kbar. Calculated slopes ?P/?T for the disproportionation reactions are ?10.7, ?24.9, ?11.2, and +7.6 bar/K for Mg₂SiO₄, Fe₂SiO₄, Co₂SiO₄, and Ni₂SiO₄. The large negative slope calculated for Fe₂SiO₄ results from a surprisingly large positive slope reported for the olivine-spinel transition in that compound (Akimoto et al., 1969). Further consideration of the systematic trends in the thermodynamics of spinel formation from the oxides suggests that the silicate spinels should have entropies of formation close to zero, resulting in values of ?P/?T which are zero or at most only slightly negative. This confirms the conclusion of Jackson, Liebermann, and Ringwood that values of ?P/?T for spinel disproportionation are unlikely to be more negative than ?10 bar/K and may well be slightly positive. Reaction of spinels to form other post-spinel phases, particularly ilmenite and perovskite, are discussed in terms of available thermochemical data.     

Melting of the silica isotypes SiO 2, BeF 2 and GeO 2 at elevated pressures

The melting curves of the structural analogues SiO ₂, BeF ₂ and GeO ₂ have been studied at pressures ?40 kbar in a piston-cylinder apparatus. The initial slopes dT_m/dP of the β-quartz-liquid boundaries for SiO ₂ and BeF ₂ are ～35° while the slope of the rutile-liquid boundary for GeO ₂ is approximately 32°C/kbar. These large values of dT/dP reflect the unusually low entropies of fusion for these compounds in which strong structural similarities exist between the crystalline phases and the melt. Implications for the extended phase diagram of silica are discussed and it is concluded that either: (1) a maximum exists on the coesite melting curve, or (2) estimates of the melting temperature of stishovite need to be revised upwards.     

Inversion of normal moveout for monoclinic media1

Multiple vertical fracture sets, possibly combined with horizontal fine layering, produce an equivalent medium of monoclinic symmetry with a horizontal symmetry plane. Although monoclinic models may be rather common for fractured formations, they have hardly been used in seismic methods of fracture detection due to the large number of independent elements in the stiffness tensor. Here, we show that multicomponent wide-azimuth reflection data (combined with known vertical velocity or reflector depth) or multi-azimuth walkaway VSP surveys provide enough information to invert for all but one anisotropic parameters of monoclinic media. In order to facilitate the inversion procedure, we introduce a Thomsen-style parametrization for monoclinic media that includes the vertical velocities of the P-wave and one of the split S-waves and a set of dimensionless anisotropic coefficients. Our notation, defined for the coordinate frame associated with the polarization directions of the vertically propagating shear waves, captures the combinations of the stiffnesses responsible for the normal-moveout (NMO) ellipses of all three pure modes. The first group of the anisotropic parameters contains seven coefficients (ε^(1,2), δ^(1,2,3) and γ^(1,2)) analogous to those defined by Tsvankin for the higher-symmetry orthorhombic model. The parameters ε^(1,2), δ^(1,2) and γ^(1,2) are primarily responsible for the pure-mode NMO velocities along the coordinate axes x₁ and x₂ (i.e. in the shear-wave polarization directions). The remaining coefficient δ⁽³⁾ is not constrained by conventional-spread reflection traveltimes in a horizontal monoclinic layer. The second parameter group consists of the newly introduced coefficients ζ^(1,2,3) which control the rotation of the P-, S₁- and S₂-wave NMO ellipses with respect to the horizontal coordinate axes. Misalignment of the P-wave NMO ellipse and shear-wave polarization directions was recently observed on field data by Pérez et al. Our parameter-estimation algorithm, based on NMO equations valid for any strength of the anisotropy, is designed to obtain anisotropic parameters of monoclinic media by inverting the vertical velocities and NMO ellipses of the P-, S₁- and S₂-waves. A Dix-type representation of the NMO velocity of mode-converted waves makes it possible to replace the pure shear modes in reflection surveys with the PS₁- and PS₂-waves. Numerical tests show that our method yields stable estimates of all relevant parameters for both a single layer and a horizontally stratified monoclinic medium.     

Geobarometry of ultramafic xenoliths from Loihi Seamount,Hawaii, on the basis of CO2 inclusions in olivine

Abundant fluid inclusions in olivine of dunite xenoliths (～1–3 cm) in basalt dredged from the young Loihi Seamount, 30 km southeast of Hawaii, are evidence for three coexisting immiscible fluid phases—silicate melt (now glass), sulfide melt (now solid), and dense supercritical CO₂ (now liquid + gas)—during growth and later fracturing of some of these olivine crystals. Some olivine xenocrysts, probably from disaggregation of xenoliths, contain similar inclusions.Most of the inclusions (2–10 μm) are on secondary planes, trapped during healing of fractures after the original crystal growth. Some such planes end abruptly within single crystals and are termed pseudosecondary, because they formed during the growth of the host olivine crystals. The “vapor” bubble in a few large (20–60 μm), isolated, and hence primary, silicate melt inclusions is too large to be the result of simple differential shrinkage. Under correct viewing conditions, these bubbles are seen to consist of CO₂ liquid and gas, with an aggregate ? = ～ 0.5–0.75 g cm^?3, and represent trapped globules of dense supercritical CO₂ (i.e., incipient “vesiculation” at depth). Some spinel crystals enclosed within olivine have attached CO₂ blebs. Spherical sulfide blebs having widely variable volume ratios to CO₂ and silicate glass are found in both primary and pseudosecondary inclusions, demonstrating that an immiscible sulfide melt was also present.Assuming olivine growth at ～ 1200°C and hydrostatic pressure from a liquid lava column, extrapolation of CO₂P-V-T data indicates that the primary inclusions were trapped at ～ 220–470 MPa (2200–4700 bars), or ～ 8–17 km depth in basalt magma of ? = 2.7 g cm^?3. Because the temperature cannot change much during the rise to eruption, the range of CO₂ densities reveals the change in pressure from that during original olivine growth to later deformation and rise to eruption on the sea floor. The presence of numerous decrepitated inclusions indicates that the inclusion sample studied is biased by the loss of higher-density inclusions and suggests that some part of these olivine xenoliths formed at greater depths.     

MnO/TiO2/P2O5: a minor element discriminant for basaltic rocks of oceanic environments and its implications for petrogenesis

A ternary diagram using MnO, TiO₂, P₂O₅ can discriminate between five petrotectonic environments of basaltic rocks (45–54% SiO₂). Fields for mid-ocean ridge, island arc tholeiite, island arc calc-alkaline, ocean island tholeiite, and ocean island alkalic rocks were distinguished on the basis of 507 analyses from well-defined environments. Boninites plot within island arc fields. Continental tholeiites, such as the Columbia River basalts, are high in P₂O₅ relative to MnO and TiO₂, and overlap portions of all five oceanic fields.MnO is depleted relative to TiO₂ in mid-ocean ridge analyses and may be controlled by early fractionation of olivine and/or clinopyroxene under conditions of lowf_O2. In island arc rocks, MnO is enriched relative to TiO₂ due to early crystallization of titanomagnetite in a high-f_O2 environment. Primitive mid-ocean ridge and arc tholeiites have similar MnO/TiO₂/P₂O₅ ratios which indicate a grossly similar parent magma. Increasingly differentiated basaltic rocks are more easily classified by the diagram. High relative abundances of TiO₂ and P₂O₅ in ocean island rocks are consistent with their derivation from a separate source.Despite the purported high mobility of MnO, the MnO/TiO₂/P₂O₅ discriminant diagram may be applied to unspilitized and moderately spilitized zeolite to greenschist facies greenstones with good agreement between the environment determined by MnO/TiO₂/P₂O₅ and by other means such as trace elements, REE, or field relations.     

新疆乌鲁木齐地区vS30经验估计研究

从新疆乌鲁木齐市2004—2015年得到的841个钻孔中选择深度达30 m以下且钻孔资料记录完整的有效钻孔123个,通过计算5~30 m范围内不同深度的等效剪切波速,分别利用线性拟合、二次拟合和三次拟合对各深度v_S（d）及其v_S30进行拟合。通过对比发现,三个方程的拟合误差都随深度的增加而减少,且三次拟合方程的误差始终小于同深度的线性拟合和二次拟合方程,因此推荐使用三次拟合方程来估计新疆乌鲁木齐市钻孔的v_S30值。同时将此结果和Boore的结果进行比较后发现,不同深度处的等效剪切波速v_S（d）和v_S30具有地域差异性;Boore得到的结果在钻孔深度小于20 m时明显高估v_S30值,拟合曲线偏离实际数据点较远,所以本文拟合结果更适用于新疆乌鲁木齐市。综合比较可知,三次拟合得到的研究结果可以为新疆乌鲁木齐市钻孔深度不足30 m的地区求解v_S30值提供参考。最后,利用新疆克拉玛依市2004—2015年钻孔资料检验三个拟合公式对克拉玛依市的适用性,发现深度越接近30 m,误差越小;线性模型和二次模型相对来说比较可靠,平均误差接近于0,并且对深度大于10 m的钻孔有高估现象;三次模型相对来说误差比较大,并且几乎在所有深度都有低估现象。     

Pyroxenes in the system Mg2Si2O6-CaMgSi2O6 at high pressure

The enstatite-diopside solvus in the system Mg₂Si₂O₆-CaMgSi₂O₆ has been experimentally determined within the pressure range 5–40 kbars and the temperature range 900–1500°C. Experiments involving reversal of the phase boundaries by unmixing from glass starting material and by reaction of pure clinoenstatite and diopside showed difficulty in achieving equilibration due to persistence of metastable, subcalcic clinopyroxene and to the sluggishness of reaction rate. The experimental data showed that the temperature dependence of the diopside limb is less than previously accepted. At 1500°C and 30 kbars subcalcic diopside found by Davis and Boyd (1966) is shown to be metastable with respect to enstatite and more calcic diopside of composition En_42.3Di_57.7. The solvus widens with increasing pressure between 5 and 40 kbars at 1200°C, but at 900°C the pressure effect on the solvus is very small. The stability relationships of the four pyroxenes, protoenstatite, enstatite, iron-free pigeonite and diopside are summarized, based on data from the literature and the present study.     

Electrical conductivity jump produced by the α-β-δ transformation in Mn2GeO4

The electrical conductivity of three polymorphs of Mn₂GeO₄ was measured under high pressures in the temperature range of 300–1200 K. It was found that the electrical conductivity increases discontinuously due to the transformation both from olivine structure (α) to modified spinel structure (β) and from β to strontium plumbate structure (δ). The amount of discontinuous change is about one half order of magnitude from α to β and one third order of magnitude from β to δ at 1200 K. In order to see the effect of the presence of iron ions, the electrical conductivity of the solid solution of (Mn_0.9Fe_0.1)₂GeO₄ was also measured. It was found that at low temperatures, where impurity conduction may be dominant, the solid solution is more conductive than the pure Mn₂GeO₄, but at high temperature no significant differences were observed between the solid solution and pure Mn₂GeO₄ in all polymorphs.A phase transformation from modified spinel structure to strontium plumbate structure is considered to be one of the plausible transformations occurring at a depth around 650 km in the earth's mantle. These experiments suggest that if this kind of transformation occurs in the mantle, some degrees of discontinuous change in electrical conductivity may be expected around 650 km.     

Temperature variation of the evolution of positive small air ions at constant relative humidity

The evolution of positive air ions is mathematically simulated considering 150 trace gases and more than a thousand ion-molecule reactions. The main attention is paid to the evolution of near-ground air ions in the age interval from 10 ms to 3 s where the knowledge about ion evolution is most limited. Recently, detailed experimental data about the time variation of the air ion mobility spectrum became available, and the results of mathematical simulation can be compared with the observed transformations. Unfortunately, the ion mobility measurements have not been accompanied by data about concentrations of the trace gases; therefore the mobilities can be interpreted only ambiguously. Nevertheless, the main features of the measured evolution shape of ions can be explained by the results of simulation, and the best agreement is achieved by the assumption of an enhanced concentration of either acetone or pyridine. In this case, the younger ions should be mainly ions H₃O⁺(H₂O)_n, while the more aged ions should be either acetone or pyridine family clusters.     

Deep pooling of low degree melts and volatile fluxes at the 85°E segment of the Gakkel Ridge: Evidence from olivine-hosted melt inclusions and glasses

We present new analyses of volatile, major, and trace elements for a suite of glasses and melt inclusions from the 85°E segment of the ultra-slow spreading Gakkel Ridge. Samples from this segment include limu o pele and glass shards, proposed to result from CO₂-driven explosive activity. The major element and volatile compositions of the melt inclusions are more variable and consistently more primitive than the glass data. CO₂ contents in the melt inclusions extend to higher values (167–1596 ppm) than in the co-existing glasses (187–227 ppm), indicating that the melt inclusions were trapped at greater depths. These melt inclusions record the highest CO₂ melt concentrations observed for a ridge environment. Based on a vapor saturation model, we estimate that the melt inclusions were trapped between seafloor depths (～ 4 km) and ～ 9 km below the seafloor. However, the glasses are all in equilibrium with their eruption depths, which is inconsistent with the rapid magma ascent rates expected for explosive activity. Melting conditions inferred from thermobarometry suggest relatively deep (25–40 km) and cold (1240°–1325 °C) melting conditions, consistent with a thermal structure calculated for the Gakkel Ridge. The water contents and trace element compositions of the melt inclusions and glasses are remarkably homogeneous; this is an unexpected result for ultra-slow spreading ridges, where magma mixing is generally thought to be less efficient based on the assumption that steady-state crustal magma chambers are absent in these environments. All melts can be described by a single liquid line of descent originating from a pooled melt composition that is consistent with the aggregate melt calculated from a geodynamic model for the Gakkel Ridge. These data suggest a model in which deep, low degree melts are efficiently pooled in the upper mantle (9–20 km depth), after which crystallization commences and continues during ascent and eruption. Based on our melting model and the assumption that CO₂ is perfectly incompatible, we show that the highest CO₂ concentrations of the melt inclusions (～ 1600 ppm) are consistent with the calculated CO₂ concentrations of primary undegassed melts. The highest measured CO₂/Nb ratio (443) of Gakkel Ridge melt inclusions predicts a mantle CO₂ content of 134 ppm and would result in a global ridge flux of 2.0 × 10¹² mol CO₂/yr.     

High-pressure disproportionation of Co2SiO4 spinel and implications for Mg2SiO4 spinel

Co₂SiO₄ spinel has been found to disproportionate into its isochemically mixed oxides with rocksalt and rutile structures at pressures between 170 and 190 kbar and temperatures between 1400 and 1800°C in a diamond-anvil press. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The slope of the phase boundary between the spinel phase and the mixed oxides is calculated to be?33 ± 20bar/deg. This negative slope is consistent with the observed anomalously large entropy of CoO (relative to its isostructural oxides) in entropy vs.(MV)^?1/2 systematics, whereM is the formula weight andV the molar volume. The sign of the slope for a phase boundary in the disproportionation of spinel depends on the values of entropy of the rocksalt oxides as well as the inverse character exhibited in the spinel phases. The normal entropy of MgO suggests that the phase boundary for the disproportionation of Mg₂SiO₄ spinel has positive slope.     

太湖有色可溶性有机物(CDOM)对COD及BOD5的指示意义

化学需氧量(COD)、五日生化需氧量(BOD_5)及溶解性有机碳(DOC)是指示湖泊水质的重要指标,然而上述指标测定通常耗费大量时间、试剂及人力物力且排放大量有害废液.有色可溶性有机物(CDOM)是溶解性有机物(DOM)中可以强烈吸收光谱中的紫外光和可见光的部分,数据测定耗时短、方便快捷,且样品处理过程环境友好,能在很大程度上反映湖泊水质.本研究基于2016年2、5和8月在太湖均匀布设的32个采样点进行样品采集,运用光谱吸收与三维荧光-平行因子分析(EEMs-PARAFAC)探究太湖CDOM的光谱吸收和荧光组分,探讨CDOM光谱指标对湖泊BOD_5、COD及DOC浓度等湖泊环境质量指标的可替代性.结果表明:(1)运用EEMs-PARAFAC方法解析出3种荧光组分:类腐殖酸C1、类酪氨酸C2和类色氨酸C3.(2) COD和BOD_5和DOC在空间上呈现出相似的分布趋势,不同水期的最高值均出现在竺山湾和梅梁湾,由西北湖区至中部敞水区、东南湖湾递减.(3)在不同水期,COD、BOD_5、DOC浓度和C1组分均表现为丰水期极显著大于枯水期和平水期,a_(254)在丰、平、枯水期间无显著性差异,最大值出现在丰水期;C2与C3组分均在枯水期和平水期极显著大于丰水期.(4)在不同水文时期,COD、BOD_5和DOC浓度均与a_(254)、类腐殖酸C1呈显著正相关,丰水期太湖COD、BOD_5和DOC浓度与CDOM光谱指标的线性相关性要优于枯水期和平水期.(5) CDOM光谱指标在不同水文时期均能很好地替代COD、BOD_5和DOC等作为反映太湖水体中有机物污染程度及湖泊水质的指标.     

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.