Eutectic temperatures and melting relations in the Fe–O–S system at high pressures and temperatures

We have investigated melting relations in the Fe–O–S ternary system in the pressure range of 15–27 GPa and 1873 K. Subsolidus phase relations are Fe, Fe₃S₂, and FeO up to 17 GPa and Fe, Fe₃S, and FeO above this pressure. The eutectic temperature slightly decreases from ambient pressure to 17 GPa, whereas increases above this pressure. The eutectic temperature in this study is 100 K lower than that in the Fe–S binary system. The oxygen content in the Fe–O–S eutectic liquid drops when the coexisting solid phases changes from FeS to Fe₃S₂. The cotectic lines in the ternary phase diagram lie close to the Fe–FeS binary axis. The isothermal sections indicate that oxygen solubility in the Fe–O–S liquid increases with increasing temperature, and with increasing sulfur content. The solubility of sulfur in the solid Fe has a maximum value at the eutectic temperature, and decreases with increasing temperature. Our results could have important implications for formation and composition of the Martian core.     

Penetration of molten iron alloy into the lower mantle phase

The core–mantle boundary is the only interface where the metallic core and the silicate mantle interact physically and chemically. Many geophysical anomalies such as low shear velocity and high electrical conductivity have been observed at the bottom of the mantle. Perturbations in the Earth's rotation rate at decadal time periods require the existence of a thin conductive layer with a conductance of 10⁸ S. Substantial additions of molten iron from the outer core into the mantle may produce these geophysical anomalies. Although iron enrichment by penetration has only been observed in (Mg,Fe)O, the second dominant mineral in the lower mantle, the penetration process leading to iron enrichment in the silicate mantle has not been experimentally confirmed. In this study, high-pressure and high-temperature experiments were conducted to investigate the penetration of molten iron alloy into lower mantle phases; postspinel, polycrystalline bridgmanite and polycrystalline (Mg,Fe)O. At the interface between (Mg,Fe)O aggregate and molten iron alloy, liquid metal penetrated the (Mg,Fe)O aggregate along grain boundaries and formed a thin layer containing metal-rich blobs. In contrast, no penetration of molten iron alloy was observed at the interface between molten iron alloy and silicate phases. Penetration of liquid iron alloy into the (Mg,Fe)O aggregate is caused by the capillarity phenomenon or Mullins–Sekerka instability. Neither mechanism occurs at the boundary of pure polycrystalline MgO, indicating that the FeO in (Mg,Fe)O plays an essential role in this phenomenon. Infiltration of molten iron alloy along grain boundaries (capillarity phenomenon) is the dominant process and precedes penetration due to the Mullins–Sekerka instability. The capillarity phenomenon is governed by the balance of forces between surface tension and gravity. In the case where the ultralow velocity zone (ULVZ) with a low shear velocity is composed of Fe-rich (Mg,Fe)O, the maximum penetration distance of molten iron alloy by capillary rise is limited to 20 m. The addition of iron-rich melt to the base of the mantle is therefore unlikely to be the main cause of the high conductance of the CMB region predicted from decadal variation of the length of day. Furthermore, the absence of molten iron alloy penetration into silicate phases does not allow an extensive modification of the chemical composition of the mantle by core–mantle interaction.     

In situ X-ray diffraction measurements of the <Emphasis Type="Italic">fcc</Emphasis>–<Emphasis Type="Italic">hcp</Emphasis> phase transition boundary of an Fe–Ni alloy in an internally heated diamond anvil cell

The phase transition boundary between the face-centered cubic (fcc) structure and hexagonal close-packed (hcp) structure in an Fe–Ni alloy was determined at pressures from 25 to 107 GPa by using an internally resistive-heated diamond anvil cell (DAC), combined with in situ synchrotron X-ray diffraction measurements. The fcc–hcp phase transition boundary in Fe–9.7 wt% Ni is located at slightly lower temperatures than that in pure Fe, confirming the previous understanding that the addition of Ni expands the stability field of the fcc phase. The dP/dT slope of the boundary was determined to be 0.0426 GPa/K, which is slightly larger than that of pure Fe. The pressure interval of the two-phase region is about 6 GPa at a constant temperature, implying that the previous estimates by laser-heated DAC experiments of 10–20 GPa were overestimated. The two-phase region of fcc + hcp would be limited to a pressure of about 120 GPa even in Fe–15 wt%Ni, excluding the possibility of the existence of the fcc phase in the inner core if the simple linear extrapolation of the two-phase region is applied. The pressure and temperature dependences of the c/a axial ratio of the hcp phase in Fe–9.7 wt% Ni are generally consistent with those in pure Fe, suggesting that Ni has minor effects on the c/a ratio.     

Experimental study of reaction between perovskite and molten iron to 146 GPa and implications for chemically distinct buoyant layer at the top of the core

Partitioning of oxygen and silicon between molten iron and (Mg,Fe)SiO₃ perovskite was investigated by a combination of laser-heated diamond-anvil cell (LHDAC) and analytical transmission electron microscope (TEM) to 146 GPa and 3,500 K. The chemical compositions of co-existing quenched molten iron and perovskite were determined quantitatively with energy-dispersive X-ray spectrometry (EDS) and electron energy loss spectroscopy (EELS). The results demonstrate that the quenched liquid iron in contact with perovskite contained substantial amounts of oxygen and silicon at such high pressure and temperature (P–T). The chemical equilibrium between perovskite, ferropericlase, and molten iron at the P–T conditions of the core–mantle boundary (CMB) was calculated in Mg–Fe–Si–O system from these experimental results and previous data on partitioning of oxygen between molten iron and ferropericlase. We found that molten iron should include oxygen and silicon more than required to account for the core density deficit (<10%) when co-existing with both perovskite and ferropericlase at the CMB. This suggests that the very bottom of the mantle may consist of either one of perovskite or ferropericlase. Alternatively, it is also possible that the bulk outer core liquid is not in direct contact with the mantle. Seismological observations of a small P-wave velocity reduction in the topmost core suggest the presence of chemically-distinct buoyant liquid layer. Such layer physically separates the mantle from the bulk outer core liquid, hindering the chemical reaction between them.     

Iron-water reaction at high pressure and temperature, and hydrogen transport into the core

We observed a direct reaction of metallic iron with water to form iron hydride and iron oxide, 3Fe + H₂O–>2FeH_x + FeO, at pressures from 6 GPa to 84 GPa and temperatures above 1,000 K in diamond anvil cell (DAC). Iron hydride is dhcpFeH_x or -FeH_x, and iron oxide has the rhombohedral or B1 structure at pressures at least up to 37 GPa. The formation of an assembly composed of dhcpFeH_x and FeO with the B8 structure was observed at 84 GPa. In primordial Earth, water formed by dehydration of the low temperature primitive materials reacts with metallic iron in the high temperature component to form iron hydride FeH_x and iron oxide FeO. The former would be incorporated in the iron forming the core. Thus hydrogen could be an important element of the Earths core. This reaction would be essential for transport of hydrogen into the core in the accretion stage of the Earth.     

Density measurements of liquid Fe–Si alloys at high pressure using the sink–float method

The compositional dependence on the density of liquid Fe alloys under high pressure is important for estimating the amount of light elements in the Earth’s outer core. Here, we report on the density of liquid Fe–Si at 4 GPa and 1,923 K measured using the sink–float method and our investigation on the effect of the Si content on the density of the liquid. Our experiments show that the density of liquid Fe–Si decreases from 7.43 to 2.71 g/cm³ non-linearly with increasing Si content (0–100 at%). The molar volume of liquid Fe–Si calculated from the measured density gradually decreases in the compositional range 0–50 at% Si, and increases in the range 50–100 at% Si. It should be noted that the estimated molar volume of the alloys shows a negative volume of mixing between Fe and Si. This behaviour is similar to Fe–S liquid (Nishida et al. in Phys Chem Miner 35:417–423, 2008). However, the excess molar volume of mixing for the liquid Fe–Si is smaller than that of liquid Fe–S. The light element contents in the outer core estimated previously may be an underestimation if we take into account the possible negative value of the excess mixing volume of iron–light element alloys in the outer core.     

Melting of iron–silicon alloy up to the core–mantle boundary pressure: implications to the thermal structure of the Earth’s core

The melting temperature of Fe–18 wt% Si alloy was determined up to 119 GPa based on a change of laser heating efficiency and the texture of the recovered samples in the laser-heated diamond anvil cell experiments. We have also investigated the subsolidus phase relations of Fe–18 wt% Si alloy by the in-situ X-ray diffraction method and confirmed that the bcc phase is stable at least up to 57 GPa and high temperature. The melting curve of the alloy was fitted by the Simon’s equation, P(GPa)/a = (T _m(K)/T ₀) ^c , with parameters, T ₀ = 1,473 K, a = 3.5 ± 1.1 GPa, and c = 4.5 ± 0.4. The melting temperature of bcc Fe–18 wt% Si alloy is comparable with that of pure iron in the pressure range of this work. The melting temperature of Fe–18 wt% Si alloy is estimated to be 3,300–3,500 K at 135 GPa, and 4,000–4,200 K at around 330 GPa, which may provide the lower bound of the temperatures at the core–mantle boundary and the inner core–outer core boundary if the light element in the core is silicon.     

Phase relations in Fe–Ni–C system at high pressures and temperatures

We performed comparative study of phase relations in Fe_1−x Ni _x (0.10 ≤ x ≤ 0.22 atomic fraction) and Fe_0.90Ni_0.10−x C _x (0.1 ≤ x ≤ 0.5 atomic fraction) systems at pressures to 45 GPa and temperatures to 2,600 K using laser-heated diamond anvil cell and large-volume press (LVP) techniques. We show that laser heating of Fe,Ni alloys in DAC even to relatively low temperatures can lead to the contamination of the sample with the carbon coming from diamond anvils, which results in the decomposition of the alloy into iron- and nickel-rich phases. Based on the results of LVP experiments with Fe–Ni–C system (at pressures up to 20 GPa and temperatures to 2,300 K) we demonstrate decrease of carbon solubility in Fe,Ni alloy with pressure.     

An experimental study of the formation of metallic iron in chondrules

The abundance of metallic iron is highly variable in different kinds of chondrites. The precise mechanism by which metal fractionation occurred and its place in time relative to chondrule formation are unknown. As metallic iron is abundant in most Type I (FeO-poor) chondrules, determining under what conditions metal could form in chondrules is of great interest. Assuming chondrules were formed from low temperature nebular condensate, we heated an anhydrous CI-like material at 1580°C in conditions similar to those of the canonical nebula (P_H2 = 1.3 × 10⁻⁵ atm). We reproduced many of the characteristics of Type IA and IIA chondrules but none of them contained any iron metal. In these experiments FeO was abundant in charges that were heated for as long as 6 h. At a lower temperature, 1350°C, dendritic/cellular metal crystallized from Fe-FeS melts during the evaporation of S. However, the silicate portion consisted of many relict grains and vesicles, not typical of chondrules.Evaporation experiments conducted at P_H2 = 1 atm and 1565°C produced charges containing metallic iron both as melt droplets and inclusions in olivine, similar to those found in chondrules. Formation of iron in these experiments was primarily the result of desulfurization of FeS. With long heating times Fe° was lost by evaporation. Apart from some reduction of FeO by kerogen to make metal inclusions within olivine grains, reduction of FeO to make Fe° in these charges was not observed.This study shows that under canonical nebular conditions FeS and iron-metal are extremely volatile so that metal-rich Type I chondrules could not form by melting “CI.” Under these conditions FeO is lost predominantly by hydrogen stripping and, due to the relative low abundance of hydrogen at low pressures, remains in the melt for as long as 6 h. Conversely, at higher total pressures (1-atm H₂) iron metal (produced mainly by the desulfurization of troilite) is less volatile and remains in the melt for longer times (at least 6 h). In addition, due to elevated pressures of hydrogen, FeO is stripped away much faster. These results suggest that chondrule formation occurred in environments with elevated pressures relative to the canonical nebula for iron metal to be present.     

The effect of sulfur content on density of the liquid Fe–S at high pressure

The density of liquid Fe–S was measured at 4 GPa and 1,923 K using a sink/float method with a composite density marker. The density marker consisted of a Pt rod core and an Al₂O₃ tube surrounding. The uncertainty in the density of the composite marker is much smaller than that of the composite sphere, which had been used in previous density measurements. The density of liquid Fe–S decreases nonlinearly with increasing sulfur content at 4 GPa and 1,923 K. This tendency is consistent with the results measured at ambient pressure. The molar volume of FeS calculated from the measured density gradually increases with sulfur content. The excess molar volume from ideal mixing of Fe and S at 4 GPa was negative value. The new method proposed here is applicable to the density measurement of other Fe alloys at high pressure. The tendency of the molar volume and the excess molar volume with sulfur content at ambient pressure is consistent with these at high pressure at least up to 4 GPa. The excess molar volume at high pressure is essential for estimating the amount of light elements in the outer core.     

Melting relationships in the system Fe-Feo at high pressures: Implications for the composition and formation of the earth's core

A reconnaissance investigation has been carried out on melting relationships in the system Fe-FeO at pressures up to 25 GPa and temperatures up to 2200° C using an MA-8 apparatus. Limited studies were also made of the Co-CoO and Ni-NiO systems. In the system FeFeO, the rapid exsolution of FeO from liquids during quenching causes some difficulties in interpretation of textures and phase relationships. The Co-CoO and Ni-NiO systems are more tractable experimentally and provide useful analogues to the Fe-FeO system. It was found that the broad field of liquid immiscibility present at ambient pressure in the Co-CoO system had disappeared at 18 GPa, 2200° C and that the system displayed complete miscibility between molten Co and CoO, analogous to the behaviour of the Ni-NiO system at ambient pressure. The phase diagram of the system Fe-FeO at 16 GPa and from 1600–2200° C was constructed from interpretations based on the textures of quenched run products. The solubility of FeO in molten iron is considerably enhanced by high pressures. At 16 GPa, the Fe-FeO eutectic contains about 10–15 mol percent FeO and the eutectic temperature in this iron-rich region of the system occurs at 1700±25° C, some 350° C below the melting point of pure iron at the same pressure. The solubility of FeO in molten Fe increases rapidly as temperature increases from 1700 to 2200° C. A relatively small liquid immiscibility field is present above 1900° C but is believed to be eliminated above 2200° C. This inference is supported by thermodynamic calculations on the positions of key phase boundaries. A single run carried out on an Fe₅₀ FeO₅₀ composition at 25 GPa and 2200° C demonstrated extensive and probably complete miscibility between Fe and FeO liquids under these conditions. The melting point of iron is decreased considerably by solution of FeO at high pressures; moreover, the melting point gradient (dP/dT) of the Fe-FeO eutectic is much smaller than that of pure iron and is also smaller than that of mantle pyrolite under the P, T conditions studied. These characteristics make it possible for melting of metal phase and segregation of the core to proceed within the Earth under conditions where most of the mantle remains below solidus temperatures. Under these conditions, the core would inevitably contain a large proportion of dissolved FeO. It is concluded therefore, that oxygen is likely to be the principal light element in the core. The inner core may not be composed of pure iron, as often proposed. Instead, it may consist of a crystalline oxide solid solution (Ni, Fe)₂O.     

同步辐射激光加温DAC技术及在地球深部物质研究中的应用

实验室模拟地球深部的温度和压力环境,研究地球相关材料的物理和化学性质,是解释地震波数据、进一步了解地球内部结构和动力学过程的重要途径。用高功率的红外激光光束,加温金刚石对顶砧压腔(DAC)中的样品,可以获得深部地幔乃至地核的极端温度和压力条件,已广泛地用于地球深部矿物的相变、熔融和状态方程研究。同步辐射微束技术的发展,为激光加温DAC技术的应用开辟了新的领域,也使地幔及地核条件下的矿物研究有了重要的突破。文章介绍激光加温DAC技术的发展;阐述高温高压原位的同步辐射X射线衍射方法;例举激光加温DAC技术在地球深部物质研究中的一些应用;并对一些关键的技术问题加以分析和讨论。     

Influence of arsenic on iron sulfide transformations

The association of arsenate, As(V), and arsenite, As(III), with disordered mackinawite, FeS, was studied in sulfide-limited (Fe:S = 1:1) and excess-sulfide (Fe:S = 1:2) batch experiments. In the absence of arsenic, the sulfide-limited experiments produce disordered mackinawite while the excess-sulfide experiments yield pyrite with trace amounts of mackinawite. With increasing initially added As(V) concentrations the transformation of FeS to mackinawite and pyrite is retarded. At S:As = 1:1 and 2:1, elemental sulfur and green rust are the end products. As(V) oxidizes S(-II) in FeS and (or) in solution to S(0), and Fe(II) in the solid phase to Fe(III). Increasing initially added As(III) concentrations inhibit the transformation of FeS to mackinawite and pyrite and no oxidation products of FeS or sulfide, other than pyrite, were observed. At low arsenic concentrations, sorption onto the FeS surface may be the reaction controlling the uptake of arsenic into the solid phase. Inhibition of iron(II) sulfide transformations due to arsenic sorption suggests that the sorption sites are crucial not only as sorption sites, but also in iron(II) sulfide transformation mechanisms.     

An alternative interpretation of lower mantle mineral associations in diamonds

Diamonds containing ferropericlase (Mg,Fe)O and other silicate (enstatite [(Mg,Fe)SiO₃], in particular) assemblages are generally believed to be derived from the Earth's lower mantle. On the basis of the observed ratio between ferropericlase and enstatite inclusions and the FeO content of these ferropericlases, it is concluded that most of these minerals entrapped in diamonds may not represent the lithology of the lower mantle itself as has been suggested by many investigators. Instead, ferropericlases in these diamonds represent most likely the disproportionate product of ferromagnesite [(Mg,Fe)CO₃], which underwent a decarbonation reaction to form both diamond and ferropericlase simultaneously in the lower mantle. The wide variation in the Mg# of ferropericlase inclusions in diamonds is attributed to the decarbonation "loop" of the MgCO₃-FeCO₃ solid solutions. Some of the enstatite inclusions coexisting with these ferropericlases in the same diamond may represent the most abundant mineral species of (Mg,Fe)SiO₃-perovskite in the lower mantle. The latter mineral phase experienced a retrogressive transition into enstatite during the transport of diamonds to the Earth's surface.     

Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

Internally consistent gahnitic spinel-cordierite-garnet equilibria in the FMASHZn system: geothermobarometry and applications

The equilibrium (Mg, Fe, Zn)₃Al₂Si₃O₁₂+2Al₂SiO₅=3(Mg, Fe, Zn)Al₂O₄+5SiO₂ garnet + sillimanite/kyanitc = spinel + quartz was calibrated in the piston-cylinder apparatus between 11 and 30 kbar, and over the temperature range of 950 to 1200°C. Three experimental mixes of Mg no. [100^*MgO/(MgO+FeO)] 40, 47 and 60, in the FeO –MgO–Al₂O₃–SiO₂–ZnO (FMASZn) system were used under low oxygen fugacities and anhydrous conditions. We derive a ternary Fe–Mg–Zn symmetric mixing model for aluminous spinels in equilibrium with garnet, to quantify the increase in gahnitic end-member of spinel with increasing pressure and descreasing temperature. Further experiments in the spinel-cordieritequartz-sillimanite field were combined with garnet-cordierite data from the literature to produce a consistent set of equations describing the exchange reactions in FMASHZn relevant to quartz-sillimanite bearing rocks at granulite facies conditions. As spinel is an important mineral participating in many rocks of aluminous composition at granulite-facies conditions, and as zinc contributes to an enlargement of spinel's stability field towards higher pressures and lower temperatures, the thermobarometric calibrations presented here will be most significant in delineating the prograde and retrograde trajectory of P-T paths.     

The binary systems FeS-MgS and FeS-MnS: Mössbauer spectroscopy of the B1 solid solutions and high-pressure phase equilibria

(Fe, Mn)S and (Fe, Mg)S solid solutions are examined to study and compare the properties of Fe²⁺ in two different B1-structured hosts, and also to study the relative stability of the B1 (NaCl) and B8 (NiAs) structures at high pressure. The Mössbauer spectra of (Fe, Mn)S and (Fe, Mg)S B1 solid solutions are quadrupole doublets at 298 K with parameters which vary smoothly with Fe²⁺ concentration. At 4.2 K the Mössbauer spectra of (Fe, Mn)S and Fe-rich (Fe, Mg)S B1 solid solutions are magnetically split into eight lines, but the spectra of Mg-rich (Fe, Mg)S solid solutions are quadrupole doublets. The line widths of the magnetic spectra are broad, consistent with a multiaxial spin arrangement. Some properties of the hypothetical phase FeS(B1) are calculated from the solid solution data; the phase is inferred to be relatively ionic compared to FeS(B8) and has a molar volume that is 7.2 percent larger than the B8 phase at 298 K. The large inferred volume difference between FeS(B1) and FeS(B8) should cause exsolution of a B8-structured phase from (Fe, Mn)S and (Fe, Mg)S B1 solid solutions at high pressure. This behaviour is confirmed experimentally at high pressure using X-ray diffraction and Mössbauer spectroscopy, and the results are correlated with thermodynamic calculations of the phase boundaries based on estimates of the volume and free energy differences between the B1 and B8 phases of FeS derived from atmospheric pressure data. The absence of an increase in solubility of Mg and Mn in the B8 phase with pressure suggests that any polymorphism in MnS and MgS at high pressure is unlikely to involve the B8 phase. Shock wave data for MgO and Fe_0.94O reported in the literature suggest similar behaviour in the system FeO-MgO at high pressure, namely exsolution of essentially pure FeO(hpp) from (Fe, Mg)O B1 solid solutions.     

Experimental study of liquid evolution in an Fe-rich,layered mafic intrusion: constraints of Fe-Ti oxide precipitation on the T-fO 2 and T-ϱ paths of tholeiitic magmas

The Newark Island layered intrusion, a composite intrusion displaying a similar fractionation sequence to the Skaergaard, has both dikes which preserved liquids fed into the intrusion and chilled pillows of liquids resident in the chamber. This study reports experimentally determined one atmosphere liquid lines of descent of these compositions as a function of oxygen fugacity which varies from QFM (quartz-fayalite-magnetite) to 0.5 log₁₀ units above IW (iron-wustite). These experiments reveal a strong oxygen fugacity dependence on the order of appearance and relative abundances of the Fe–Ti oxide minerals. Titanomagnetite saturates prior to ilmenite at QFM, but the order is reversed at lower oxygen fugacities. In the layered series of the Newark Island intrusion, ilmenite arrives shortly before titanomagnetite and the titanomagnetite/ilmenite ratio decreases monotonically after the cumulus appearance of titanomagnetite. Comparison of the crystallization sequence in the intrusion with that of the experiments requires that the oxygen fugacity in the intrusion increased relative to QFM before titanomagnetite saturation and decreased afterward, but always remained between the QFM and IW buffers. Similar trends in the modes of the Fe–Ti oxides (ilmenite and titanomagnetite) in the Skaergaard, Kiglapait, and Somerset Dam intrusions along with Fe₂O₃/FeO ratios in MORBs suggest that such a temperature-oxygen fugacity path may be typical of tholeiitic magma differentiation. Calculations of the temperature-density paths of the experimental liquids indicate that, at all possible oxygen fugacities, the density must have decreased abruptly after Fe–Ti oxide saturation. Accordingly, liquids replenishing the intrusion after Fe–Ti oxide saturation should pond at the bottom of the chamber, quenching against older cumulates. Field observation at the Newark Island intrusion confirm this prediction. The similarities in the fractionation paths of several other layered intrusions to that of the Newark Island intrusion suggest that the density of the liquids in these intrusions also decreased after Fe–Ti oxide saturation. Experiments on a suggested initial Skaergaard liquid are consistent with this model.     

The composition of the Earth

Compositional models of the Earth are critically dependent on three main sources of information: the seismic profile of the Earth and its interpretation, comparisons between primitive meteorites and the solar nebula composition, and chemical and petrological models of peridotite-basalt melting relationships. Whereas a family of compositional models for the Earth are permissible based on these methods, the model that is most consistent with the seismological and geodynamic structure of the Earth comprises an upper and lower mantle of similar composition, an Fe---Ni core having between 5% and 15% of a low-atomic-weight element, and a mantle which, when compared to CI carbonaceous chondrites, is depleted in Mg and Si relative to the refractory lithophile elements.The absolute and relative abundances of the refractory elements in carbonaceous, ordinary, and enstatite chondritic meteorites are compared. The bulk composition of an average CI carbonaceous chondrite is defined from previous compilations and from the refractory element compositions of different groups of chondrites. The absolute uncertainties in their refractory element compositions are evaluated by comparing ratios of these elements. These data are then used to evaluate existing models of the composition of the Silicate Earth.The systematic behavior of major and trace elements during differentiation of the mantle is used to constrain the Silicate Earth composition. Seemingly fertile peridotites have experienced a previous melting event that must be accounted for when developing these models. The approach taken here avoids unnecessary assumptions inherent in several existing models, and results in an internally consistent Silicate Earth composition having chondritic proportions of the refractory lithophile elements at 2.75 times that in CI carbonaceous chondrites. Element ratios in peridotites, komatiites, basalts and various crustal rocks are used to assess the abundances of both non-lithophile and non-refractory elements in the Silicate Earth. These data provide insights into the accretion processes of the Earth, the chemical evolution of the Earth's mantle, the effect of core formation, and indicate negligible exchange between the core and mantle throughout the geologic record (the last 3.5 Ga).The composition of the Earth's core is poorly constrained beyond its major constituents (i.e. an Fe---Ni alloy). Density contrasts between the inner and outer core boundary are used to suggest the presence ( 10 ± 5%) of a light element or a combination of elements (e.g., O, S, Si) in the outer core. The core is the dominant repository of siderophile elements in the Earth. The limits of our understanding of the core's composition (including the light-element component) depend on models of core formation and the class of chondritic meteorites we have chosen when constructing models of the bulk Earth's composition.The Earth has a bulk Fe/Al of 20 ± 2, established by assuming that the Earth's budget of Al is stored entirely within the Silicate Earth and Fe is partitioned between the Silicate Earth ( 14%) and the core ( 86%). Chondritic meteorites display a range of Fe/Al ratios, with many having a value close to 20. A comparison of the bulk composition of the Earth and chondritic meteorites reveals both similarities and differences, with the Earth being more strongly depleted in the more volatile elements. There is no group of meteorites that has a bulk composition matching that of the Earth's.     

上天、入地、下海:极端条件下矿物学研究

上天、入地、下海,进行极端条件下的矿物学研究,研究微矿物,发现新矿物。主要利用金刚石压机,结合使用国内外同步辐射X-光源、中子源,以及其他多种物理的、化学的、光学的测试手段(如岩石矿物化学分析,光薄片测定,电子探针,离子探针,扫描电镜,透射电镜,红外、紫外、拉曼光谱,激光加热等),对来自天外的陨石、陨石坑样品、地球深处地幔源矿物以及海底甲烷水合物进行了一些研究。模拟不同温度和压力下各种不同成分的矿物材料的晶体结构、物理和化学性质。文章着重研究从地球内核到地壳海底的各种不同组分在不同温度、压力极端环境下形成的各种各样的典型矿物:从金属固体内核和金属液体外核中的ε-Fe到核幔边界(CMB)地球D″层的后钙钛矿(Post-Perovskite)结构(ppv)镁铁硅酸盐(Mg,Fe)SiO₃,从下地幔中的铁磁性钙钛矿(Perovskite)结构(pv)镁铁硅酸盐布里奇曼石(Bridgmanite)(Mg,Fe)SiO₃、镁铁氧化物(Fe,Mg)O和后尖晶石(Post-Spinel)结构的含Fe³⁺毛河光矿(Maohokite)(HP-Mg$Fe^{3+}_{2}O_{4}$)到过渡带、上地幔和地壳中的镁铁硅酸盐、硅氧化物、铬铁氧化物和金刚石及其内含物以及甲烷水合物(CH₄·H₂O)等。进行高温高压极端条件下的矿物学研究,为探索地球结构性质、形成动力和发展历史提供了新的窗口。