地球深部碱性元素地球化学行为:来自陨石高压矿物的证据

近年来在球粒陨石冲击脉体中陆续发现了一些天然高压新矿物和矿物组合，这些发现为地球深部碱性元素的地球化学行为的研究提供了重要依据。在地幔过渡带温度和压力条件下，钠和钙离子优先结合到镁铁－镁铝榴石固溶体和长石高压多形之中，钾离子则选择性地进入到长石高压多形中，副矿物涂氏磷钙石是Na、Ba、Sr和轻稀土等元素的潜在载体相。天然冲击变质球粒陨石为我们提供了探索过渡带和下地幔温度、压力条件下碱性元素载体相特征的重要自然界样品。     

天然高压矿物研究的新进展及其在地幔矿物学中的意义

对地表陨石坑岩石和陨石的冲击变质效应的研究, 是以往发现天然高压矿物的主要途径。α-PbO2 超斯石英、(Na,K,Ca)AlSi3O8-锰钡矿以及磷灰石高压同质多像变体等是几个近期在陨石中发现的天然高压相,这些高压相很可能存在于地幔之中。天然高压矿物的发现对地幔矿物学研究和发展起了推动作用。     

从随州陨石研究探讨地幔的高压矿物组成

随州陨石母体在30 Ma前遭遇一次其他星体的撞击后,矿物发生了冲击变质作用,产生了几条宽度仅为0.02～0.09 mm的冲击熔脉.我们在随州陨石熔脉内和熔脉边部先后发现了多种冲击成因的高压相矿物,如粗粒的、由固态相变形成的林伍德石、低钙辉石的镁铁榴石相、钛铁矿相和钙钛矿玻璃相、NaAlSi3O8-锰钡矿相、涂氏磷钙石和铬铁矿的两种后尖晶石高压多形—CaFe2O4结构相和CaTi2O4结构相（其中后三种为首次发现的高压相新矿物）,以及细粒的、在高压下从硅酸盐熔体结晶的镁铁榴石-镁铝榴石固溶体、镁方铁矿和林伍德石微晶集合体.此外,在陨石主体中还见有斜长石的高压熔体相—熔长石.熔长石和多种高压相矿物的存在,限定了随州陨石主体所受压力、温度分别为20 GPa和1100℃,熔脉内则高达23～25 GPa和2000～2300℃.上述撞击产生的压力与地球内部地幔转换带下部到下地幔顶部的压力相当.大量天然产出的高压相矿物在随州陨石中的发现,对了解深部地幔的矿物组成和元素地球化学行为具有重要理论意义.     

动态高压下陨石矿物的冲击熔融和分离结晶及其地球化学意义

应用近代微束矿物学分析测试技术,对在中国陨落的随州、寺巷口和岩庄等三块球粒陨石中矿物的冲击熔融和分离结晶作用进行了较系统的研究。查明存在有硅酸盐单矿物熔体、硅酸盐矿物混合熔体和全岩熔体三种组成不同的冲击熔体。研究结果显示:(1)三种熔融相与未熔相之间在主成分和微量元素组成上没有明显差别,说明它们是原地熔融的产物,但在较大的冲击熔块中,也发现冲击熔融作用引发了一部分元素,如亲铁元素、硒元素和轻重稀土元素的分异现象;(2)查明Al2O3、Cr2O3、Na2O和CaO等优先进入从冲击熔体结晶的辉石常压相或辉石的高压相——镁铁榴石(属地幔过渡带矿物)中;(3)Al元素能进入阿基莫石(即辉石的钛铁矿结构相,属下地幔矿物)中,以固熔体形式稳定下来。ELNES的测定查明,其氧化铁组分中Fe3+/∑Fe的比值高达0.67(3);(4)陨石全岩熔体中硅酸盐相与金属-硫化物相之间为完全不混熔,后者以孤立的共结体团块产于硅酸盐熔体之中,除Zn、Na、Cr、Co和Cu在硫化物相中和Na在金属相中有明显富集外,其他元素的浓度则无明显变化;(5)在寺巷口陨石熔脉的金属-硫化物共结团块内发现了FeNi金属-硫化铁-磁铁矿组合,进一步证实了S和O等轻元素可以加入到以Fe-Ni金属为主要组成的地核成分中去;(6)在岩庄陨石的FeNi金属-硫化铁共结体团块的硫化铁内发现了Na、Mn和Fe的磷酸盐矿物小球体,说明P和Na、Mn等元素也能成为地核的组成元素。以上研究在行星演化、地幔矿物学和地球化学,以及陨石学研究上均有着重要的科学意义。     

陨石中林伍德石的形成条件对寻找地球产状林伍德石的启示

橄榄石高压多形林伍德石被认为是地幔过渡带的主要矿物。天然产状林伍德石主要在发生强烈冲击变质的球粒陨石冲击脉体中出现。目前还没有在地球岩石中发现林伍德石的报告。陨石冲击脉体的温度压力历史和矿物组合特征研究表明,林伍德石形成后,高压下淬火是使林伍德石不发生退变作用的重要条件。陨石中有利于林伍德石保存的淬火时间仅为数秒到十多秒。在地球上任何地质事件中,均难以实现在如此短的时问内使位于地幔过渡带的林伍德石被带往地球表层。寻找地球产状的林伍德石,关键是要在岩石和矿物中存在有利于林伍德石保存的条件,特别是当这些岩石和矿物仍处于高温的环境时。     

南极陨石GRV 022115冲击熔融脉矿物学研究

文章主要通过电子探针、扫描电镜、激光拉曼光谱、透射电镜等微区微分析技术研究GRV 022115球粒陨石的基础矿物学特征和冲击变质矿物学特征，探讨陨石冲击熔融脉的形成机制和界定其母体的冲击条件。陨石主岩主要由橄榄石、辉石、熔长石、铁镍金属和硫化物等矿物组成。根据主岩的硅酸盐矿物学特征，确定GRV 022115是风化程度较低（W1） 的L6型普通球粒陨石，与前期分类结果一致。根据熔融脉内含有大量林伍德石的现象，修正GRV 022115陨石的冲击级别为S6，比原定的S5高一个级别。GRV 022115球粒陨石中有多条冲击熔融脉，熔融脉由基质和主岩碎块包裹体两类岩相组组成。熔融脉基质的主要组成是微米级粒状镁铁榴石与纳米级的含铁方镁石，是在平衡冲击压力下结晶的产物。冲击熔融脉主岩碎块包裹体中的橄榄石、低钙辉石、长石碎块已部分或全部转为相对应的高压相。橄榄石相变为林伍德石；个别低钙辉石相变为钙钛矿结构布里奇曼石微晶的集合体；长石主要相变为熔长石与玲根石。几乎所有的主岩碎块都有高温熔融的圆滑边界。熔融脉内外同类矿物的主量和微量元素具有一定的差异性，该差异性可以反映高温高压下混溶作用和扩散作用的影响。结合陨石冲击熔融脉形成机制和结晶模型，根据熔脉基质中镁铁榴石+方镁石矿物组合及静态高温高压实验相图，界定该陨石经受的冲击压力为23~27 GPa。     

地幔中水的存在形式和含水量

水以含水变质矿物、无水硅酸盐矿物(橄榄石、辉石等)及其高压结构相(β橄榄石、γ橄榄石、钙钛矿相、方镁铁矿等)、高密度含水镁硅酸盐和熔体的形式存在于地幔各层圈中。根据各类玄武岩水含量推断出的上地幔源区的水含量,和由地幔岩主要矿物———橄榄石的水含量估算出的上地幔水含量(质量分数)很接近,在0.02%左右。以橄榄石和辉石高压相的水含量为依据,进行了过渡带和下地幔水含量的估算,其结果是:过渡带和下地幔上部的水含量(质量分数)为1.48%,下地幔下部水含量(质量分数)为0.21%。据此,计算出的地幔各层圈的总水量表明,地幔水的74%以上存在于过渡带和下地幔上部。将地幔总水量和现代海洋总水量之和作为地球总水量,计算出现代海洋总水量约占全球总水量(质量分数)的6.6%,这个结果与笔者根据地球的球粒陨石成分模型计算出的总水量(6%)十分接近。     

大洋地幔橄榄岩-铬铁矿中的金刚石和深地幔再循环

全球多地蛇绿岩型地幔橄榄岩和铬铁矿中发现微粒金刚石，并在中国西藏南部和俄罗斯乌拉尔北部的蛇绿岩铬铁矿中发现原位产出的金刚石，认为是地球上金刚石的一种新的产出类型，不同于金伯利岩型金刚石和超高压变质型金刚石。它们与呈斯石英假象的柯石英、高压相的铬铁矿和青松矿等高压矿物以及碳硅石和单质矿物等强还原矿物伴生，指示蛇绿岩中的这些矿物组合形成于深度150~300 km或者更深的地幔。金刚石具有很轻的C同位素组成（δ13C-18‰~-28‰），并出现多种含Mn矿物和壳源成分包裹体。研究认为它们曾是早期深俯冲的地壳物质，达到>300 km深部地幔或地幔过渡带后，经历了熔融并产生新的流体，后者在上升过程中结晶成新的超高压、强还原矿物组合，通过地幔对流或地幔柱作用被带回到浅部地幔，由此建立了一个俯冲物质深地幔再循环的新模式。蛇绿岩型地幔橄榄岩和铬铁矿中发现金刚石等深部矿物，质疑了蛇绿岩铬铁矿形成于浅部地幔的已有认识，引发了一系列新的科学问题，提出了新的研究方向。      

涂氏磷钙石的形成条件研究

用微束矿物学和激光拉曼光谱等分析测试技术,并结合人工高压实验结果,研究了我国随州陨石冲击熔脉中的白磷钙石高压相变形成涂氏磷钙石的必要条件,并对寺巷口陨石冲击熔脉中的白磷钙石虽与林伍德石、镁铁榴石和玲根石等高压矿物共生,但仅表现为结构损伤而未相变成涂氏磷钙石的原因进行了探讨.研究结果发现,随州陨石中白磷钙石或氯磷灰石的存在是涂氏磷钙石得以形成的物质前提,陨石熔脉中高达24 GPa和2000℃以上的高压高温环境是涂氏磷钙石能够形成的条件保障,而压力释放后熔脉极快的冷却速率是涂氏磷钙石得以淬火并稳定保存的关键.研究还查明,寺巷口陨石冲击熔脉比随州陨石的熔脉要宽1至2个量级,其冷却速率比随州陨石慢得多,因此,熔脉中早先形成的涂氏磷钙石,可能在脉内较高的冲击后温度影响下,慢慢退变质成白磷钙矿.     

超高压矿物研究进展

我国超高压矿物研究近十年来取得了重要进展.参与发现了5个超高压新矿物及若干待命名高压相,被国际矿物协会新矿物、命名与分类委员会批准和命名的超高压矿物包括涂氏磷钙石、塞石英、玲根石、谢氏超晶石、阿考寨石等.在冲击变质陨石中发现了后尖晶石结构的超高压相,即谢氏超晶石和CF相,引起了高压地质学及大地构造学界的关注.揭示了从冲击成因二氧化硅熔体中结晶的柯石英,合理地限定了冲击变质成因柯石英的形成压力温度条件,为我国首个地外天体撞击构造——岫岩陨石坑的证实提供了关键的矿物物理证据.     

Classification of 24 New Ordinary Chondrites from the Grove Mountains, Antarctica

Petrography and mineral chemistry of 24 ordinary chondrites from the Grove Mountains, Antarctica, have been studied in order to identify their chemical-petrographic types. These samples were selected from a total of 4448 Grove Mountains (GRV) meteorites collected during the 19th Chinese Antarctic Research Expedition so as to make an estimation of the large GRV meteorite collection. The chemical-petrographic types of these meteorites are presented below: 1 H3,2 H4, 4 H5, 2 H6, 1 L4, 7 L5, 5 L6, 1 LL4 and 1 LL6. The new data weaken the previous report that unequilibrated ordinary chondrites are unusually abundant in the Grove Mountains region. However, this work confirms significant differences in distribution patterns of chemical-petrographic types between the Grove Mountains and other     

Early solar system processes recorded in the matrices of two highly pristine CR3 carbonaceous chondrites, MET 00426 and QUE 99177

The mineralogy and bulk compositions of the matrices of the CR chondrites MET 00426 and QUE 99177 have been studied using a combination of SEM, EPMA, and TEM techniques. The matrices of these two chondrites are texturally, chemically, and mineralogically similar and are characterized by significant FeO-enrichments with respect to other CR chondrite matrices, nearly flat refractory lithophile patterns, variable volatile element patterns, and a simple mineral assemblage dominated by amorphous silicate material and Fe,Ni sulfides. Fine-grained, crystalline silicate phases such as olivine and pyroxene appear to be extremely rare in the matrices of both meteorites. Instead, the mineralogy of matrices and fine-grained rims of both meteorites consists of abundant amorphous FeO-rich silicate material, containing nanoparticles of Fe,Ni sulfides (troilite, pyrrhotite, and pentlandite). Secondary alteration minerals that are characteristic of other CR chondrites (e.g., Renazzo and Al Rais), such as phyllosilicates, magnetite, and calcite are also rare. The texture and mineralogy of the matrices of MET 00426 and QUE 99177 share many features with matrices in the primitive carbonaceous chondrites ALH A77307 (CO3.0) and Acfer 094 (unique). These observations show that MET 00426 and QUE 99177 are very low petrologic type 3 chondrites that have escaped the effects of aqueous alteration, unlike other CR chondrites, which are typically classified as petrologic type 2. We suggest that these meteorites represent additional samples of highly primitive, but extremely rare carbonaceous chondrites of petrologic type 3.00, according to the classification scheme of Grossman and Brearley (2005). The highly pristine nature of MET 00426 and QUE 99177 provides important additional insights into the origins of fine-grained materials in carbonaceous chondrites. Based on our new observations, we infer that the amorphous silicate material and nanosulfide particles that dominate the matrices of these meteorites formed in the solar nebula by rapid condensation of material following high-temperature events, such as those that formed chondrules.     

陨石矿物种类的研究进展和矿物表

早在约 2 0 0年前 ,科学家就在铁陨石中鉴定出了两种陨石矿物——陨硫铁和金属铁—镍。到了 1 9世纪 80年代 ,陨石矿物的数量增加到 1 6种。 2 0世纪 60年代以来 ,随着显微镜的广泛应用 ,以及许多新的测试技术如 X射线衍射、电子探针、扫描电镜和透射电镜的应用 ,使更多的陨石矿物能被发现。1 967年 ( Mason列出 60种陨石矿物 )至 1 987年( Yudin和 Kolomenskiy列出了 2 0 0种陨石矿物 )的2 0年间陨石矿物种数增加到原来的 3倍多。1 991年Ulyanov完成了陨石、星际尘粒和玻璃陨石共 350种矿物的列表。Rubin〔1〕在前人工作的基础上 ,去掉…     

Infrared reflection spectrometry analysis as a non‐destructive method of characterizing minerals and stone materials in geoarchaeological and archaeometric applications

The purpose of this paper is to show the benefits and applications of using mid and far infrared reflection spectrometry (IRS) in the analysis of archaeological materials. Infrared spectral databases do not yet exist for rocks and principal minerals. In support of IRS techniques, a catalogue and new spectral database have been created with over 500 infrared reflection spectra in mid and far ranges from more than 250 different archaeological minerals and stone materials. The reflection spectrum serves as a “fingerprint” of all these materials. This new, non‐destructive method is useful for spectrometric identification and crystal chemical characterization of many rocks and minerals commonly found in archaeological contexts. Three brief examples of IRS analysis of archaeological materials are presented as test cases. It is suggested that IRS could and should become a routine approach in geoarchaeology and archaeometry for identification and provenance studies. © 2009 Wiley Periodicals, Inc.     

X射线粉晶衍射法在变粒岩鉴定与分类中的应用

变粒岩的鉴定通常以显微镜鉴定技术为主,但在显微镜下区分颗粒细小的长石、石英及绿泥石、蒙脱石、云母等层状硅酸盐矿物十分困难,仅通过显微鉴定技术对变粒岩进行定名可能产生较大误差,这对地质填图和原岩恢复工作会造成一些偏差,导致得出错误的地质结论。随着X射线衍射分析技术的发展,该技术已广泛应用于矿物学和岩石学的研究,本研究将结合X射线粉晶衍射技术,对显微镜下难以区分的细小矿物进行鉴定。共选用23件变粒岩样品,利用X射线粉晶衍射分析和显微镜岩石薄片鉴定技术,对变粒岩矿物组分进行检测,用X射线粉晶衍射矿物半定量分析结果验证岩石薄片鉴定结果准确性。显微镜岩石薄片鉴定结果与X射线粉晶衍射物相分析结果对比显示,10件样品定名一致,其余13件样品详细定名有差异。通过分析产生差异的原因,可以认为显微镜岩石薄片鉴定优势在于能确定岩石结构和构造,以及常见矿物组分;X射线粉晶衍射法的优势在于能检测出显微镜下较难区分的细小石英和长石颗粒的相对含量,并能检测出颗粒较小的绿泥石、蒙脱石及云母等层状硅酸盐矿物,该方法对含量较少、颗粒较细的矿物检测效果较好。实验证明将显微岩石薄片鉴定技术和X射线粉晶衍射技术相结合,才能更准确对变粒岩进行定名,为地学研究提供更符合客观实际的技术数据和分析结论。     

The petrogenesis of L-6 chondrites: insights from the chemistry of minerals

Major, minor and trace element concentrations have been measured in all the volumetrically significant minerals from the L-6 chondrites Alfianello, Colby (WI) and Leedey. Most of the elements show the compositional uniformity observed in other studies. However, REE, Co and Ni are distinctly different in their abundances and their phase distributions in each of the three meteorites. Such differences must manifest differing physical and chemical conditions involved in the formation of each of the three rocks. The distributions of REE and Ni between various phases are compatible with models which assume equilibrium between presently coexisting minerals. Such a model demonstrates how plausible differences in temperature and Ni content of metallic minerals could produce the observed differences in Ni abundances in olivine and clinopyroxene from each of the three chondrites.REE are too abundant in the minerals to have been produced by crystal-liquid fractionation from a magma of whole rock composition.Alkali element abundances are incompatible with a model of closed system equilibration of the meteorites. Rb is underabundant in feldspar relative to Na when compared to the equilibrium model predictions. A portion of the Cs seems to be included in feldspar by diadochic substitution, however, significant amounts are randomly associated with other minerals, perhaps by incorporation into lattice defects and at interstices. Partial loss of this nonfeldspathic Cs may be responsible for the large range of Cs abundances observed in chondrites.     

The unequilibrated enstatite chondrites

The enstatite chondrites formed under highly reducing (and/or sulfidizing) conditions as indicated by their mineral assemblages and compositions, which are sharply different from those of other chondrite groups. Enstatite is the major silicate mineral. Kamacite is Si-bearing and the enstatite chondrites contain a wide variety of monosulfide minerals that are not present in other chondrite groups. The unequilibrated enstatite chondrites are comprised of two groups (EH3 and EL3) and one anomalous member (LEW 87223), which can be distinguished by differences in their mineral assemblages and compositions. EH3 chondrites have >1.8 wt.% Si in their kamacite and contain the monosulfide niningerite (MgS), whereas EL3 chondrites have less than 1.4 wt.% Si in their kamacite and contain the monosulfide alabandite (MnS). The distinct mineralogies, compositions and textures of E3 chondrites make comparisons with ordinary chondrites (OCs) and carbonaceous chondrites (CCs) difficult, however, a range of recrystallization features in the E3s are observed, and some may be as primitive as type 3.1 OCs and CCs. Others, especially the EL3 chondrites, may have been considerably modified by impact processes and their primary textures disturbed. The chondrules in E3 chondrites, although texturally similar to type I pyroxene-rich chondrules, are sharply different from chondrules in other chondrite groups in containing Si-bearing metal, Ca- and Mg–Mn-rich sulfides and silica. This indicates formation in a reduced nebular environment separate from chondrules in other chondrites and possibly different precursor materials. Additionally the oxygen isotope compositions of E3 chondrules indicate formation from a unique oxygen reservoir. Although the abundance, size distribution, and secondary alteration minerals are not always identical, CAIs in E3 chondrites generally have textures, mineral assemblages and compositions similar to those in other groups. These observations indicates that CAIs in O, C and E chondrites all formed in the reservoir under similar conditions, and were redistributed to the different chondrite accretion zones, where the secondary alteration took place. Thus, chondrule formation was a local process for each particular chondrite group, but all CAIs may have formed in the similar nebular environment. Lack of evidence of water (hydrous minerals), and oxygen isotope compositions similar to Earth and Moon suggest formation of the E chondrites in the inner solar system and make them prime candidates as building blocks for the inner planets.     

吉林陨石中橄榄石和辉石的化学成份特征兼谈平衡球粒陨石中的不平衡性

吉林陨石中的球粒分为正常快速冷却和过冷冷却球粒两种。前一类球粒中的橄榄石和辉石的化学成份相对稳定,代表了平衡球粒陨石的特征。后一类球粒中的橄榄石和辉石不仅在总的化学成份上有别于前者,而且矿物本身成份不稳定,反映了平衡球粒陨石中存在着不平衡性。     

新矿物与新矿物研究创新探索

作为矿物学的重要基础研究方向之一,新矿物的发现及其晶体结构、晶体化学的研究始终备受各发达国家的一贯重视。新矿物的研究和发现及其成果具有国际性,在一定程度上反映了国家在该领域以及整体科技水平和对科学发现的贡献。笔者近年来参与了对若干存疑矿物进行的精细晶体结构与晶体化学研究和矿物学研究,从2005年至今参与发现的23种新矿物均获得国际矿物学协会新矿物及分类命名委员会(IMA-CNMNC)所批准。这些新矿物的获批得益于成功地获取了成分数据、衍射数据和晶体结构的阐明。本文就新矿物的认定规则、申报内容和数据、分类命名、研究内容及工作方法等进行综述,在此抛砖引玉,希望通过交流促进我国新矿物研究领域的发展。     

Rhodium, gold and other highly siderophile element abundances in chondritic meteorites

The abundances of the highly siderophile elements (HSE) Re, Os, Ir, Ru, Pt, Rh, Pd and Au, and ¹⁸⁷Os/¹⁸⁸Os isotope ratios have been determined for a set of carbonaceous, ordinary, enstatite and Rumuruti chondrites, using an analytical technique that permits the precise and accurate measurement of all HSE from the same digestion aliquot. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS analysis. The monoisotopic elements Rh and Au were quantified relative to the abundance of Ir.Differences in HSE abundances and ratios such as Re/Os, ¹⁸⁷Os/¹⁸⁸Os, Pd/Ir and Au/Ir between different chondrite classes are further substantiated with new data, and additional Rh and Au data, including new data for CI chondrites. Systematically different relative abundances of Rh between different chondrite classes are reminiscent of the behaviour of Re. Carbonaceous chondrites are characterized by low average Rh/Ir of 0.27 ± 0.03 (1s) which is about 20% lower than the ratio for ordinary (0.34 ± 0.02) and enstatite chondrites (EH: 0.33 ± 0.01; EL: 0.32 ± 0.01). R chondrites show higher and somewhat variable Rh/Ir of 0.37 ± 0.07.Well-defined linear correlations of HSE, in particular for bulk samples of ordinary and EL chondrites, are explained by binary mixing and/or dilution by silicates. The HSE carriers responsible for these correlations have a uniform chemical composition, indicating efficient homogenization of local nebular heterogeneities during or prior to the formation of the host minerals in chondrite components. Excepting Rumuruti chondrites and Au in carbonaceous chondrites, these correlations also suggest that metamorphism, alteration and igneous processes had negligible influence on the HSE distribution on the bulk sample scale.Depletion patterns for Rh, Pd and Au in carbonaceous chondrites other than CI are smoothly related to condensation temperatures and therefore consistent with the general depletion of moderately volatile elements in carbonaceous chondrites. Fractionated HSE abundance patterns of ordinary, enstatite and Rumuruti chondrites, however, are more difficult to explain. Fractional condensation combined with the removal of metal phases at various times, and later mixing of early and late formed metal phases may provide a viable explanation. Planetary fractionation processes that may have affected precursor material of chondrite components cannot explain the HSE abundance patterns of chondrite groups. HSE abundances of some, but not all Rumuruti chondrites may be consistent with solid sulphide-liquid sulphide fractionation processes during impact induced melting.