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。     

西藏蛇绿岩中不寻常的地幔矿物群

在西藏雅鲁藏布江蛇绿岩的铬铁矿中，首次发现由100余种（亚种）矿物组成的地幔矿物群，其中包括：自然元素，合金，氧化物，硫（砷）化物和硅酸盐。根据实验资料，其中一部分是超高压成因矿物。可能来自地球核-幔边界，是地球外核与下地幔底部硅酸盐之间化学反应的产物，另一部分矿物可能来自下地幔，过渡带和上地幔。西藏地幔矿物群，无论在矿物学和地球动力学上均有重要意义。     

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。     

西藏蛇绿岩的超高压矿物：FeO、Fe、FeSi、Si和SiO2组合及其地球动力学意义

在西藏雅鲁藏布江蛇绿岩带的东段，出露罗布莎蛇绿岩块和豆荚状铬铁矿床。从豆荚状铬铁矿石中查明60－70种伴生矿物，其中包含FeO、Fe、FeSi、Si和SiO2组合。根据超高压－高温实验，该组合应形成于地球外核与下地幔之间的D“层，是地球外核的液态铁与镁硅酸盐钙钛矿（MgSiO3)相互化学反应的产物。西藏该超高压矿物组合揭示了蛇绿岩地幔活动可能深达地球外核。罗布莎蛇绿岩的该矿物组合可能是地幔－外地核之间的产物，或者是被对流作用，亦是被起源于D“层的地幔柱活动带到上地幔的。铬铁矿在地幔中结晶，并捕获了该矿物组合。     

地幔底层及其在全球物质演化中的意义

在核幔界面之上的下地幔一侧,地震波速分布极不均匀,厚度在50~300 km范围内变化的一层物质称为地幔底层。地幔底层由具有高地震波速和高密度的D″区和超低速带(ULVZ)组成。地幔底层是地核热能向地幔传播的必经之路,也是地幔中温度和温度梯度最高的地区。地幔底层既是俯冲板块的最终归宿,又是热柱和超级热柱的源区。因此,地幔底层既是全地幔对流的起点,又是全地幔对流的终点。在地幔底层可能发生地幔物质(包括俯冲板块物质在内)的部分熔融作用,也可能存在外核液态铁与地幔硅酸盐的化学反应。所以地幔底层在全球物质演化中占有重要的地位。     

下地幔及核幔边界结构及地球动力学

新一代高分辨率下地幔及核幔边界的地震层析成像,改变了我们对全球构造模式及地球动力过程的认识。古海洋岩石圈板片一直俯冲到下地幔底部,其残留体在核幔边界积累,并支持了地幔整体对流模式。位于核幔边界上的D″层有着十分复杂而精细的结构。紧靠核幔边界的地幔一侧发现了超低速层(ULVZ),它们可能是D″层内的局部熔融物,是引起地表热点的上升地幔柱的源头。     

下地幔矿物研究及其进展

文中综述了20世纪90年代以来对下地幔矿物高温高压研究的进展,详细评论了下地幔温压下(Mg,Fe)SiO3钙钛矿的稳定性、(Mg, Fe)SiO3 钙钛矿和(Mg, Fe)O镁方铁矿的高压状态方程和热弹性及高压熔化、核幔边界温压下铁和硅酸盐的化学反应等几个热点问题;探讨了下地幔的矿物学组成,对下地幔的地震波速异常给出了可能的矿物学解释;介绍了国内同领域的研究工作;展望了下地幔矿物研究的发展方向。     

地球氧逸度

地球是一个"氧化性"的星球。在太阳系所有行星中,只有地球大气中含有高浓度的O_2(约占21%)。研究表明,地球演化的早期,其大气组成与火星等类地行星相似,都是以CO_2为主,O_2含量可以忽略不计。在大约24-21亿年前,地球大气中O_2含量突然大幅度升高,一度超过现今O_2含量的1%,而后又在中元古代回落到现今O_2含量的0.1%以下。沉积物中氧化还原敏感元素的含量变化显示,大约6.3亿年前雪球地球结束之后,地球大气中的O_2含量再次大幅度升高至20%左右,而后在显生宙经历一系列复杂变化并最终演化至现今的水平。Re/Os比值显示,硅酸盐地球的氧逸度远高于月球,也高于火星。考虑到月球与地球分异发生在45亿年前,月球的低氧逸度暗示地球早期的氧逸度可能也较低。可以影响地球氧逸度的元素主要有O、H、Fe、S和C等。控制地球氧逸度变化的主要过程包括:核幔分异、板块俯冲和火山喷发去气等。在核幔分异以前,金属Fe可能是控制硅酸盐地球及其表生环境低氧逸度的关键因素。核幔分异过程中,Fe是控制氧逸度变化的关键元素。核幔分异将金属Fe与铁氧化物分开,造成地幔Fe~(3+)/Fe~(2+)比值升高。尤其是在下地幔,Fe~(2+)在高压下发生歧化反应,形成金属Fe和Fe~(3+)。其中Fe~(3+)赋存在布里奇曼石中,导致下地幔氧逸度低。在板块俯冲过程中,当有板片进入下地幔时,布里奇曼石会因体积补偿,被运移到上地幔,并发生分解,释放出Fe~(3+),导致周围地幔氧逸度的升高。但是,V/Sc和Zn/Fe等元素比值则显示在过去30多亿年以来,地幔的氧逸度变化不大,可能与上、下地幔间氧化还原缓冲层或者是上述元素比值对氧逸度不够敏感有关。在地球演化早期,金刚石是最早形成的矿物。由于金刚石的密度在上地幔高于地幔橄榄岩熔体,而在下地幔小于地幔橄榄岩熔体,因此在岩浆海阶段,金刚石倾向于在上地幔底部富集,成为一个富金刚石的储层。在板块俯冲阶段,这些金刚石会被布里奇曼石分解所释放的Fe~(3+)所氧化,形成富碳酸盐和CO:的层位,同时起到稳定上地幔氧逸度的作用。俯冲带地幔橄榄岩和岛弧火山岩的氧逸度均高于板内环境,因此一般认为板块俯冲会导致氧逸度升高。在板块俯冲过程中,氧逸度主要受到Fe和H_2O(水分解释放出H_2)的控制。蚀变大洋岩石圈中含有大量的H_2O,板块俯冲过程中脱水会导致地幔楔蛇纹石化。蛇纹石化过程会形成磁铁矿,释放出味,使局部在短时间内氧逸度降低。但是,由于H_2很容易逸散到大气中,而磁铁矿则保留在地幔楔中,其结果导致岩石中Fe~(3+)/Fe~(2+)比值升高,从而在发生部分熔融时形成高氧逸度岩浆。板块俯冲对氧逸度的影响是多方面的,还与俯冲板块的年龄、沉积物的性质等有关。对于富含有机物的沉积物俯冲过程,C是主要的氧逸度控制元素。在板块俯冲的浅部,有机物分解,释放出CH_4等还原性气体,造成上覆岩石圈氧逸度下降。富含铁锰结核等氧化性沉积物的俯冲则可以导致地幔楔氧逸度的升高,这一过程中Fe和Mn是控制氧逸度的主要元素。火山喷发可以释放出CH_4、CO_2、H_2S和SO_2等气体,也可以影响大气中O_2的含量。有研究认为,火山气体中的H_2S随岩浆房压力增加而增加,SO_2则随压力的增加而减少,因此岩浆房压力可以影响其排气的氧化-还原性,进而影响大气的O_2含量。一种观点认为,正是由于太古宙末期大量出现陆相火山岩,导致了大氧化事件,在这一模型中,S是控制氧逸度的关键。氧逸度对多种成矿作用均具有重要的控制作用。其中,斑岩铜金矿床的形成往往与高氧逸度的埃达克岩有关。这是由于当岩浆的氧逸度高于AFMQ+1.5时,岩浆中S主要以硫酸盐的形式存在。由于硫酸盐在岩浆中的溶解度远远高于硫化物,因此,在俯冲洋壳部分熔融过程中形成的高氧逸度埃达克质岩浆可以熔出更多的亲硫元素,有利于成矿。锡矿床的形成则往往与还原性岩浆有关。这是因为在高氧逸度岩浆中,Sn主要呈Sn~(4+),易于在岩浆结晶早期进入矿物中;而在还原性岩浆中,Sn主要以Sn~(2+)形式存在,表现为不相容元素,倾向于在岩浆中富集,并在岩浆期后热液阶段富集成矿。其他氧化还原敏感元素,如U、V、Mo、Re、Sb和Fe等,可以在表生过程中富集,有利于进一步富集成矿。     

地幔氧逸度的时空变化

地幔氧逸度是反映地幔氧化还原程度的参量,由温度、压力、岩石化学成分、矿物结构等共同作用控制。目前对上地幔氧逸度的研究主要针对镁橄榄石-磁铁矿-石英体系、含角闪石的橄榄岩体系和玄武岩(熔体)体系,通过实验岩石学方法进行。地幔氧逸度在垂直深度上随深度增加而减小受到普遍认可。天然样品和理论研究认为,岩石圈地幔底部的软流圈氧逸度高于上部岩石圈地幔,垂直方向上地幔氧逸度存在逆梯度,地幔过渡带相对上地幔可能也存在类似情况;水平方向上,不同构造环境、相似构造环境的不同地区氧逸度之间的差异都指示地幔氧逸度存在水平不均一性。不同圈层之间物质交换和氧逸度变化的关系是氧逸度未来研究的重点之一。俯冲带是研究圈层之间物质交换和氧逸度变化关系的天然实验室,同时氧逸度反过来也影响着各种挥发性元素(如C、S等)在不同圈层之间的赋存形式和循环通量。     

地球上地幔中氧逸度的控制因素

尽管近年来在这方面取得了重大进展,但围绕着地球上地幔中的氧逸度(fo_2)以及缓冲该氧逸度的化学反应还有很大的争议.电化学测量结果表明上地幔中氧化状态不均一,其中一组数据靠近铁橄榄石—磁铁矿—石英(FMQ)缓冲线,另一组靠近铁一方铁矿—(IW)缓冲线.根据玄武质玻璃、幔源尖晶石、钛铁矿、石榴石中Fe~(3+)/Fe~(2+)比值进行的温压计算,表明氧化状态很均一,限定于方铁矿—磁铁矿(WM)缓冲线与FMQ缓冲线之间.我们在这里根据共存矿物的成分,对比了4种“氧压力计”的行为,这4各种压力计中包括了在适合于上地幔压力、温度和成分的条件下在尖晶石二辉橄榄岩中经实验校正的一种新的橄榄石—斜方辉石—尖晶石经验压力计.将这一压力计应用于不同构造环境中的幔源岩石和玄武质熔体,所得结果表明与地幔仅仅微弱地受FE~(3+)/Fe~(2+)平衡所缓冲.较氧化的地壳物质的再徨过程以及地壳物质注入适度还厚、缓冲条件很差的软流圈,控制着氧逸度结构的大规模不均一性.     

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.     

Dynamics and evolution of the deep mantle resulting from thermal,chemical, phase and melting effects

The core–mantle boundary (CMB) – the interface between the silicate mantle and liquid iron alloy outer core – is the most important boundary inside our planet, with processes occurring in the deep mantle above it playing a major role in the evolution of both the core and the mantle. The last decade has seen an astonishing improvement in our knowledge of this region due to improvements in seismological data and techniques for mapping both large- and small-scale structures, mineral physics discoveries such as post-perovskite and the iron spin transition, and dynamical modelling. The deep mantle is increasingly revealed as a very complex region characterised by large variations in temperature and composition, phase changes, melting (possibly at present and certainly in the past), and anisotropic structures. Here, some fundamentals of the relevant processes and uncertainties are reviewed in the context of long-term Earth evolution and how it has led to the observed present-day structures. Melting has been a dominant process in Earth's evolution. Several processes involving melting, some of which operated soon after Earth's formation and some of which operated throughout its history, have produced dense, iron rich material that has likely sunk to the deepest mantle to be incorporated into a heterogeneous basal mélange (BAM) that is now evident seismically as two large low-velocity regions under African and the Pacific, but was probably much larger in the past. This BAM modulates core heat flux, plume formation and the separation of different slab components, and may contain various trace-element cocktails required to explain geochemical observations. The geographical location of BAM material has, however, probably changed through Earth's history due to the inherent time-dependence of plate tectonics and continental cycles.     

Reactions of iron with calcium carbonate at 6 GPa and 1273–1873 K: implications for carbonate reduction in the deep mantle

Experimental data on Fe-CaCO₃ interaction at 6 GPa and 1273–1873 K are presented. The system models the hypothetical redox interaction in subducting slabs at the contact with the reduced mantle and a putative process at the core-mantle boundary. The reaction is accompanied by carbonatite melt formation. It also produces Fe3C and calcium wustite, which form solid or liquid phases depending on experimental conditions. In iron-containing systems at 6 GPa, calcium carbonate melts in the range 1473–1573 K, which is consistent with aragonite disappearance from complex carbonate systems. The composition of calcium carbonate liquid is not influenced by metallic Fe. It corresponds to nearly pure CaCO₃. Along the mantle adiabat or at slightly higher temperatures, nearly pure CaCO₃ coexists with metallic iron or calcium wustite. This hypothesis explains the coexistence of metallic iron and carbonate inclusions in lithospheric and superdeep diamonds.     

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.     

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。     

Pre-eruption history of phyric basalts from DSDP legs 45 and 46: Evidence from morphology and zoning patterns in plagioclase

Phyric basalts recovered from DSDP Legs 45 and 46 contain abundant plagioclase phenocrysts which occur as either discrete single grains (megacrysts) or aggregates (glomerocrysts) and which are too abundant and too anorthitic to have crystallized from a liquid with the observed bulk rock composition. Almost all the plagioclase crystals are complexly zoned. In most cases two abrupt and relatively large compositional changes associated with continuous internal morphologic boundaries divide the plagioclase crystals into three parts: core, mantle and rim. The cores exhibit two major types of morphology: tabular, with a euhedral to slightly rounded outline; or a skeletal inner core wrapped by a slightly rounded homogeneous outer core. The mantle region is characterized by a zoning pattern composed of one to several spikes/plateaus superimposed on a gently zoned base line, with one large plateau always at the outside of the mantle, and by, in most cases, a rounded internal morphology. The inner rim is typically oscillatory zoned. The width of the outer rim can be correlated with the position of the individual crystal in the basalt pillow. The presence of a skeletal inner core and the concentration of glass inclusions in low-An zones in the mantle region suggest that the liquid in which these parts of the crystals were growing was undercooled some amount. The resorption features at the outer margins of low-An zones indicate superheating of the liquid with respect to the crystal.It is proposed that the plagioclase cores formed during injection of primitive magma into a previously existing magma chamber, that the mantle formed during mixing of a partially mixed magma and the remaining magma already in the chamber, and that the inner rim formed when the mixed magma was in a sheeted dike system. The large plateau at the outside of the mantle may have formed during the injection of the next batch of primitive magma into the main chamber, which may trigger an eruption. This model is consistent with fluid dynamic calculations and geochemically based magma mixing models, and is suggested to be the major mechanism for generating the disequilibrium conditions in the magma.     

Reaction between liquid iron and (Mg,Fe)SiO3-perovskite and solubilities of Si and O in molten iron at 27 GPa

The Earth’s core contains light elements and their identification is essential for our understanding of the thermal structure and convection in the core that drives the geodynamo and heat flow from the core to the mantle. Solubilities of Si and O in liquid iron coexisting with (Mg,Fe)SiO₃-perovskite, a major constituent of the lower mantle, were investigated at temperatures between 2,320 and 3,040 K at 27 GPa. It was observed that Si dissolved in the liquid iron up to 1.70 wt% at 3,040 K and O dissolved in the liquid iron up to 7.5 wt% at 2,800 K. It was also clearly seen that liquid iron reacts with (Mg,Fe)SiO₃-perovskite to form magnesiowüstite and it contains Si and O at 27 GPa and at 2,640 and 3,040 K. The amounts of Si and O in the liquid iron are 1.70 and 2.25 wt% at 3,040 K, respectively. The solubilities of Si and O in liquid iron coexisting with (Mg,Fe)SiO₃-perovskite have strong positive temperature dependency. Hence, they can be plausible candidates for the light elements in the core.     

地球内核与地球深部动力学

地球内核由外核富含铁元素的液态物质结晶而成。经证实,内核正以约１（°）／ａ的速率相对于地幔向东转动。内核的旋转是通过穿过内核的地震波的走时随时间变化推测得到的。这种变化是最近十多年来揭示出的内核各向异性在空间方位的改变所造成。内核的各向异性被认为起因于各向异性的铁晶体的有序排列,但这种有序排列的机制还不清楚。内核在地球发电机中起着重要的作用。利用大型的并行计算机,人们已得到能产生像地磁场一样的三维发电机数值模拟。地震学观测到的内核差速旋转为最近的发电机数值模拟提供了支持。这种数值模拟曾预测：导体内核与外核产生的磁场的电磁耦合驱动了内核每年几度向东旋转。地核通过核幔边界的接触及内核与地幔的引力耦合与地幔存在强烈的相互作用。多学科领域的突破为认识地球的深部动力过程提供了极好的机会和手段。