钙钛矿型硅酸盐的热膨胀及地幔分层

位于地下670公里深处的地震不连续带是上、下地幔的分界面,其压强为24GPa,温度为2—3千K。在这样的条件下,上地幔的主要矿物——橄榄石〔(Mg、Fe)_2SiO_4〕、辉石〔(Mg、Fe)SiO_3〕和石榴石〔(Mg、Fe、Ca)_3Al_2Si_2O_2〕将转变为斜方畸变的具钙钛矿结构的〔(Mg、Fe)SiO_3〕矿物或以钙钛矿为主的矿物组合。由于钙钛矿型的硅酸盐至少在70GPa压力下还是稳定的,因而它被认为是下地幔(或许是整个地球)中最主要的矿物。尽管钙钛矿型的硅酸盐很重要,但直到1976年才被发现,而且由于合成这种矿物所需的压力和温度条件很难达到,所以对其物理性质还不甚了解。例如,钙钛矿热膨胀系数对下地幔可能存在的成分模式起着重要的制约作用。最近我们合成了足够量的钙钛矿型的(Mg_0.9,Fe_0.1)SiO_2以便用X射线衍射法测定其在温度达840K时的无压热膨胀。在高温下测得的平均热膨胀系数为4×10~(-6)K~(-1)。这么大的热膨胀系数表明:根据土地幔组分(如地幔岩或石榴石橄榄岩,Mg值≈0.89)的标准模式求得的无压密度,要比推断的下地幔在无压条件下的密度低大纣2%。这一结果显示:上地幔与下地幔的化学性质是不同的;这与地幔热对流的分层模式是一致的。     

下地幔布里基曼石的铁自旋态及其地球物理意义

<正>根据地幔岩模型,下地幔主要由于布里基曼石[(Mg,Fe)(Fe,Si,Al)O3)]、铁方镁石[(Mg,Fe)O]、Ca-钙钛矿组成。Badro et al.,2003利用X光发射光谱发现,下地幔铁方镁石中的铁在高压下会经历电子的自旋转变[1]。随即发现,铁在下地幔矿物中的自旋转变会带来一系列物理性质的改变,如密度、弹性模量、波速、热传导系数以及电导率等[2]。在过去的十几年中,研究铁在下地幔矿物中的自旋态,以及自旋转变对下地     

地幔过渡带和下地幔组成与深部热源研究进展

受时空不可及性的制约,地质学家在探究地球深部物质组成方面仍显得很被动,尤其是在探究地幔物质组成方面显得更加艰难.目前,科学家们探测地幔物质主要依靠地球物理学和实验矿物学、岩石学方法相结合的手段来进行.结果表明,地幔过渡带主要的矿物组成有瓦士利石、林伍德石、超硅石榴子石以及少量的CaSiO3.下地幔主要矿物组成有钙钛矿(Pv)、后钙钛矿(PPv)和镁方铁矿(Mw).在讨论过渡带和下地幔物质组成的基础上,归纳总结了地球内部热源的三种来源,分别是放射性元素的衰变热和初始熔融硅酸盐地球长期冷却放出的热、核幔边界在地磁场和高电导率物质的作用下产生的热以及来自地核的热.这些结论对研究地球深部动力学和热力学过程有重要意义.     

地球下地幔矿物结构和热力学参数的研究进展与展望

下地幔从660 km到2 891 km深度,占据整个地球质量的49.2%并处于极端高温高压的状态。在下地幔相应的温度压力条件下研究主要构成矿物的物理性质,尤其是结构、密度和波速,是理解下地幔结构、物质组成以及动力学过程的关键。通过回顾过去30年高温高压矿物学实验对下地幔矿物,包括布里基曼石、铁方镁石、Ca-钙钛矿以及硅酸盐—后钙钛矿结构和热力学状态方程的重要研究进展,探讨温压条件变化、成分变化以及Fe自旋变化对这些下地幔矿物(相)密度和体波波速的影响,指出现有研究结果的不足和需要解决的问题,并对未来的研究方向提出展望。     

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。     

下地幔温压下(Mg, Fe)SiO3钙钛矿的相稳定性

在69～100 GPa冲击压力(估算温度为2600～4300 K)范围内进行了初始样品为(Mg0.92, Fe0.08)SiO3顽火辉石和MgO+SiO2的冲击压缩回收实验。对回收样品进行的X射线衍射(XRD)分析结果表明: 两发顽火辉石回收样品的主相均是单链状结构硅酸盐, 而非钙钛矿结构; 另外, 回收样品中均未观察到氧化物SiO2 和(Mg0.92, Fe0.08)O的XRD特征谱线; 两发MgO+SiO2回收样品中均观察到SiO2和镁橄榄石(Mg2SiO4)而没有氧化物MgO。实验结果表明: 在冲击压缩过程中样品处于钙钛矿结构, 在冲击卸载过程中样品发生了由钙钛矿结构向单链状结构的逆转相变; 在实验的温压范围内, 不可能发生由(Mg0.92, Fe0.08)SiO3向SiO2和(Mg0.92, Fe0.08)O的化学分解相变, 顽火辉石的高压相——钙钛矿结构是稳定的。高压加载或卸载过程引起的晶格畸变导致回收样品和原始样品的谱线差异, 而高压加载导致钙钛矿型(Mg0.92, Fe0.08)SiO3晶格畸变的可能性更大。     

下地幔方镁铁矿自旋转变的研究进展

压力引起的铁的电子自旋转变发生在下地幔的主要矿物中,这种转变对下地幔矿物的力学、物理学和化学等性质都会产生重要影响,因此在下地幔温度、压力条件下开展下地幔主要矿物相的自旋转变研究对下地幔地球物理学、地球化学和地球动力学等模型的约束具有重要意义。作为下地幔矿物质量分数第2的方镁铁矿,前人对其自旋转变以及这种转变对它的密度、声速、弹性性质、铁的分配、辐射热传导和电导率等的影响有广泛研究。本文旨在对方镁铁矿的自旋转变的主要研究进展进行总结和评述,并对未来该研究的发展趋势进行展望。     

西藏罗布莎蛇绿岩地幔岩中首次发现超高压矿物方铁矿和自然铁

在西藏雅鲁藏布江蛇绿岩带的东部,距拉萨市200km的罗布莎蛇绿岩的豆荚状铬铁岩中,发现方铁矿和自然铁。而且以自然铁为核心并包裹于方铁矿中,两者形成圆球形态。自然铁的空间群为Fm3m,晶胞参数a=0．28663nm。方铁矿空间群为Fm3m,晶胞参数a=0．43070nm。根据有关实验资料推断,高压矿物方铁矿和自然铁来自下地幔,并且可能为核幔边界化学反应生成物。     

下地幔CaSiO3钙钛矿的稳定性及其对LLSVPs的启示

LLSVPs的成因是当前固体地球科学研究的前沿热点,对这一成因的认识仍然存在很大的争议。认识LLSVPs的成因,对了解全球地幔对流性质、下地幔热结构以及化学物质的运输和演化等具有重要的科学意义。CaSiO₃钙钛矿（Ca-Pv）作为下地幔最丰富的矿物之一,也是近年来学术界关注的热点。Ca-Pv在下地幔条件下的晶体结构仍然是目前研究的主要问题之一,Ca-Pv能否与其结构和化学式都相近的含铁布里奇曼石形成固溶体?本文通过第一性原理地球化学计算,研究了Ca-Pv及固溶体的基态稳定性,弹性性质和地震波波速特性。研究结果表明,在20～120 GPa压力下,Ca-Pv最稳定的基态结构为四方结构。基态下Ca-Pv的弹性波速值低于Mg-Pv约5%。与非互溶体系相比,x（Fe）为0%～10%的固溶体体系,引起了-2%～0%的剪切波波速负异常;-1.2%～0%的纵波波速负异常;-0.45～0.15%的体波速异常。因此,推测固溶体Mg_1-x-yCa_xFe_ySiO₃可能作为下地幔LLSVPs的候选矿物组...     

下地幔矿物及生成条件

据CatherineMcCammon等报道,在巴西Luiz河发现的金刚石中含有一些矿物包裹体,其中有（Mg,Fe,Al）（Si,Al）O3,（Mg,Fe）O,CasiO3和四面体的铁铝-镁铝榴石混合物（tetragonalalmandine－pyropephase,下简称为TAPP）,通过研究其氧化状态,就能了解一些下地幔的信息。含有包裹体的金刚石来自下地幔。通过对其内部包裹体周围的微裂隙检查,包裹体内部矿物压力测定及同位素研究,可以证明金刚石在后来的地质作用中未改变其化学成分。包裹体中的（Mg,Al）（Si,Al）O3在下地幔可能以钙钛矿的形式存在,而TAPP则是其原始相。…     

Low Mantle Perovskite: Solid Solution,Spin State of Iron and Water Solubility

Silicate perovskites((Mg, Fe)SiO 3 and CaS iO 3) are believed to be the major constituent minerals in the lower mantle. The phase relation, solid solution, spin state of iron and water solubility related to the lower mantle perovskite are of great effect on the geodynamics of the Earth's interior and on ore mineralization. Previous studies indicate that a large amount of iron coupled with aluminum can incorporate into magnesium perovskite, but this is discordant with the disproportionation of(Mg,Fe)SiO 3 perovskite into iron-free MgS i O3 perovskite and hexagonal phase(Mg0.6Fe0.4)SiO 3 in the Earth's lower mantle. MnS iO 3 is the first chemical component confirmed to form wide range solid solution with Ca SiO 3 perovskite and complete solid solution with MgS i O3 perovskite at the P-T conditions in the lower mantle, and addition of Mn Si O3 will strongly affects the mutual solubility between Mg Si O3 and CaS iO 3. The spin state of iron is deeply depends on the site occupation of the Fe3+or Fe2+, the synthesis and the annealing conditions of the sample. It seems that the spin state of Fe2+ in the lower mantle perovskite can be settled as high spin, however, the existence of intermediate spin or low spin state of Fe2+ in perovskite has not been clarified. Moreover, different results have also been reported for the spin state of Fe3+ in perovskite. The water solubility of the lower mantle perovskite is related with its composition. In pure Mg SiO 3 perovskite, only less than 500 ppm water was reported. Al–Mg Si O3 perovskite or Al–Fe–MgS iO 3 perovskite in the lower mantle accommodates water of 1100 to 1800 ppm. Further experiments are necessary to clarify the detailed conditions for perovskite solid solution, to reliably analyze the valence and spin states of iron in the coexisting iron-bearing phases, and to compare the water solubility of different phases at different layers for deeply understanding the geodynamics of the Earth's interior and ore mineralization.     

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.     

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.     

深源地震机理的新认识──反向裂隙断层作用

高温高压实验究表明，地幔矿物相交与深源地震有着密切的关系。在具有放热效应的橄榄石一尖晶石相变过程中形成的反向裂隙（ａｎｔｉｃｒａｃｈ）是诱发深源地震的主要原因；而发生在下地幔的相变作用（例如钛铁矿－钙钛矿相变）因其具有吸热效应的特征，不形成反向裂隙，从而导致深源地震终止于下地幔顶界。     

大陆下地壳拆沉模式初探

下地壳拆沉是人们关注的问题,文中指出下地壳拆沉必须满足至少三个条件：（1）地壳加厚使其下部达到熘辉岩相是拆沉的前提.（2）大规模岩浆活动使大量低密度的中酸性物质移出下地壳,使下地壳密度增加直至超过下伏地幔.由于下地壳榴辉岩石部分熔融所形成的岩浆具有埃达克岩的地球化学特征,因此,大规模魂达克岩的熔出是下地壳拆沉的先决和必要条件.（3）岩石圈地幔转化为软流圈地幔,使下地壳能够进入地幔.陆壳下的岩石圈地幔原先是冷的、刚性的和不易流动的，如果有热和水的加入，可以被软化，使其变成热的、塑性的和易流动的软流圈地幔。因此，岩石圈了幔转化为软流圈地幔是下地壳拆沉的必要条件。作者认为，下地壳不大可能整体拆沉，而很可能是一块一块如飘雪花似地拆沉。如果下地壳的密度降低（低于下伏地幔），如果地幔停止热的供给，如果陆壳底部的软流圈地幔幔又恢复为岩石圈地幔，拆沉即终止。文中讨论了中国东部中生代下地壳拆沉的可能性，探讨了岩石圈减薄的机制，认为下地壳不需要也不可能与岩石圈地幔一道拆况。     

Melting relations and major element partitioning in an oxidized bulk Earth model composition at 15–26 GPa

Melting experiments were performed on an FeO-rich bulk Earth model composition in the CMFAS system in order to investigate the partitioning of major elements between coexisting minerals and melts. The starting material (34.2% SiO₂, 3.86% Al₂O₃, 35.2% FeO, 25.0% MgO and 1.88% CaO), contained in Re-capsules, was a mixture of crystalline forsterite and fayalite, and a glass containing SiO₂, Al₂O₃, and CaO. Olivine is the first liquidus phase at 10 GPa but is replaced by majoritic garnet (ga) in the 15–26 GPa range. Magnesiowüstite (mw) crystallizes close to the liquidus and is joined by perovskite (pv) at 26 GPa.

The quenched melt compositions are homogeneous throughout the melt region of the charges and are only slightly enriched in Si, Ca and Fe, and depleted in Mg, relative to the starting composition. The Fe/Mg and Ca/Al ratios in all of the minerals increase rapidly below the liquidus to become compatible with the bulk composition at the solidus. At 26 GPa, a relative density sequence of mw>pv>melt>ga is observed. This indicates that majorite floating, combined with the sinking of magnesiowüstite and perovskite can be expected during the solidification of a Hadean magma ocean and in hot mantle plumes early in the Earth's history. The mineral–melt partitioning relations indicate that fractional crystallization or partial melting in the transition zone and the upper part of the lower mantle would increase the Fe/Mg and Ca/Al ratios of the melt, even if magnesiowüstite was predominant in the solid fraction. A significant contribution of accumulated mw to the segregation of the protocore is therefore unlikely. The suggested process of perovskite fractionation to the lower mantle is not capable of increasing the Mg/Si ratio in the residual melt, and the combined fractionation of perovskite and magnesiowüstite produces a melt with elevated ratios of Si/Mg, Ca/Al and Fe/Mg.     

Hydration and dehydration in the lower margin of a cold mantle wedge: implications for crust–mantle interactions and petrogeneses of arc magmas

Garnet orthopyroxenites from Maowu (Dabieshan orogen, eastern China) were formed from a refractory harzburgite/dunite protolith. They preserve mineralogical and geochemical evidence of hydration/metasomatism and dehydration at the lower edge of a cold mantle wedge. Abundant polyphase inclusions in the cores of garnet porphyroblasts record the earliest metamorphism and metasomatism in garnet orthopyroxenites. They are mainly composed of pargasitic amphibole, gedrite, chlorite, talc, phlogopite, and Cl-apatite, with minor anhydrous minerals such as orthopyroxene, sapphirine, spinel, and rutile. Most of these phases have high X_Mg, NiO, and Ni/Mg values, implying that they probably inherited the chemistry of pre-existing olivine. Trace element analyses indicate that polyphase inclusions are enriched in large ion lithophile elements (LILE), light rare earth elements (LREE), and high field strength elements (HFSE), with spikes of Ba, Pb, U, and high U/Th. Based on the P–T conditions of formation for the polyphase inclusions (?1.4 GPa, 720–850°C), we suggest that the protolith likely underwent significant hydration/metasomatism by slab-derived fluid under shallow–wet–cold mantle wedge corner conditions beneath the forearc. When the hydrated rocks were subducted into a deep–cold mantle wedge zone and underwent high-pressure–ultrahigh-pressure (HP–UHP) metamorphism, amphibole, talc, and chlorite dehydrated and garnet, orthopyroxene, Ti-chondrodite, and Ti-clinohumite formed during prograde metamorphism. The majority of LILE (e.g. Ba, U, Pb, Sr, and Th) and LREE were released into the fluid formed by dehydration reactions, whereas HFSE (e.g. Ti, Nb, and Ta) remained in the cold mantle wedge lower margin. Such fluid resembling the trace element characteristics of arc magmas evidently migrates into the overlying, internal, hotter part of the mantle wedge, thus resulting in a high degree of partial melting and the formation of arc magmas.     

岚皋金云角闪辉石岩类捕虏体特征

陕西岚皋地区碱质基性超基性潜火山杂岩中的金云角闪辉石岩类捕虏体，主要由透辉石、富钛韭闪石、高Ｔｉ金云母、磷灰石及钛铁矿组成。捕虏体发育三联晶、碎裂边、扭折变形等固相线下变形变质结构，与正常地幔尖晶石二辉橄榄岩成分相比，捕虏体富ＴｉＯ２、Ｆｅ２Ｏ３、ＣａＯ、Ｎａ２Ｏ、Ｋ２Ｏ，贫ＭｇＯ；其稀土元素具富集特征，尤其富集ＬＲＥＥ；微量元素配分型式显示富亲石不相容元素的特征。岩相学、矿物学及岩石化学特征表明，该类捕虏体为交代地幔捕虏体，它代表了北大巴山早古生代裂谷作用时期的异常地幔。交代营力可能源于地幔热柱的上升，在地幔深处可能以熔体交代作用为主，往上逐渐以流体交代作用为主     

Prediction of high-temperature oxygen isotope fractionation factors between mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of ¹⁸O-enrichment: pyroxene (Mg,Fe,Ca)₂Si₂O₆>olivine (Mg,Fe)₂SiO₄>spinel (Mg,Fe)₂SiO₄>ilmenite (Mg,Fe, Ca)SiO₃>perovskite (Mg,Fe,Ca)SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) system are in excellent agreement with experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in ¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in ¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle would essentially result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth's interior can be described by the following sequence of ¹⁸O-enrichment: uppr crust>lower crust>upper mantle>transition zone>lower mantle >core.