山东金伯利岩中新发现的柱红石亚族矿物──K-Cr柱红石──上地幔含大阳离子Cr、Ti、Fe氧化物矿物研究之二

在山东蒙阴金伯利宕的副矿物蒙山矿中，首次发现了成分为柱红石类的新矿物相。对其成分进行探针分析，其一般晶体化学式可写为：A1.499～1.787B1.548～2,317C5.675～6.354O16。其中，A＝K、Ba、Na、La；B＝Cr、Fe、Mg、V；C＝Ti、Zr、Nb等，平均计算化学式为：（K1.256Ba0.241Na0.085La0.046）1.628（Cr1.817Fe0.321Mg0.085V0.093）1.816（Ti6.015Zr0.075Nb0.039）6.119O16．理想化学式K2Cr2Ti6O16；相当于Redledgeite（BaCr2Ti6O16）[1]的K端元，且与南非OrangeFree州StarMine及NewEland新发现的K－Ba－Vtitanates（钛酸盐）[2，3]具有成分上的可比性。为使柱红石亚族矿物的命名系统化，本文采用主要大阳离子（K、Ba）与变价元素（Fe、Cr、V）为端元组分的命名原则，将新种命名为K－Cr柱红石。根据国外资料对柱红石亚族矿物Redlcdgeite的成分修正[1,4]建议将其原中文译名“硅镁铝钛矿”[5,6]更正为“Ba－Cr柱红石”。新种与蒙阴近年来发现的沂蒙矿、蒙山矿一起，组成了含大阳离子及硅酸盐不相容元素的复杂钛铬铁氧化物组合，皆以K、Cr为特征，从而与南非以Ba为主，含V的这类矿物形成区域对比。     

我国金伯利岩中发现的蒙山矿

蒙山矿(Mathiasite)——(K,Ba)(Ti,Cr,Fe,Mg)_(21)O_(38)是1979年研究我国金伯利岩中镁钛铁矿和沂蒙矿时发现的,并曾作过报道。我国金伯利岩中蒙山矿的发现对进一步深入研究金伯利岩伴生副矿物的标型特征及其成因条件提供了新资料。现将初步研究结果报告如下.     

沂蒙矿种新成员——新矿物钙沂蒙矿亚种的发现及产出特征

沂蒙矿是中国1980年发现的新矿物,采用电子探针对采自山东蒙阴金伯利岩胜利一号小岩管中的沂蒙矿类矿物进行了分析,确定了沂蒙矿的Ca端元矿物--钙沂蒙矿(暂定名),是又一个被确定的新矿物.该新矿物简化的矿物化学式为:Ca0.5～1.0(Fe,Mg,Cr,Ti)14～15O19.钙沂蒙矿与(K)沂蒙矿、富钡沂蒙矿共生,沿镁钛矿-尖晶石出溶体呈板片状条带分布,均为交代成因.3种不同成分的沂蒙矿颗粒均十分细小,颗粒总数达100粒左右,但钙沂蒙矿产出不多.与其他沂蒙矿不同,钙沂蒙矿在结晶学A位置上几乎全为Ca,少有其他大阳离子;在结晶学B位置上二价阳离子(Fe2 、Mg)占三分之二.最后从沂蒙矿晶体结构的角度讨论了钙沂蒙矿在自然界不易产出的原因.     

新发现的沂蒙矿类质同象系列矿物：K（Ti5Fe3Cr2Mg2）12O19及Ba（…

在山东蒙阴金伯利岩中，首次发现了沂蒙矿类质同象系列新的富Ｔｉ矿物（变）种。理想的晶体化学式可表达为：Ｋ（Ｔｉ５Ｆｅ３Ｃｒ２Ｍｇ２）１２Ｏ１９（简称Ｋ－Ｔｉ沂蒙矿）（Ｂａ，Ｋ）（Ｔｉ５Ｆｅ４Ｍｇ２Ｃｒ）１２Ｏ１９（简称Ｂａ－Ｔｉ沂蒙矿）从而与原来确定的沂蒙矿Ｋ（Ｃｒ５Ｔｉ３Ｆｅ２Ｍｇ２）１２Ｏ１９和钡钛铁铬矿（Ｂａ，Ｋ）（Ｃｒ４Ｆｅ４Ｔｉ３Ｍｇ）１２Ｏ１９ｇ一起构成了金伯利岩中ＡＭ１２Ｏ１９磁铁铅矿     

山东金伯利岩蒙山矿(mathiasite)研究的新进展──上地幔含大阳离子Cr、Ti、Fe氧化物矿物研究之三

本文回顾了国内外金伯利岩及其它地幔岩中发现的K、Ba、Ca、REE的Ti-Cr－Fe－Mg氧化物矿物的研究现状，包括沂蒙矿系列、蒙山矿系列及柱红石系列。在此基础上概括性地总结了笔者近一、二年对山东蒙阴金伯利岩中蒙山矿矿物所进行的微区矿物学方向研究取得的最新进展，包括：①揭示了K、Ba、Ca、REE等半径较大的元素在蒙山矿中的不均匀分布特点；②首次在金伯利岩中发现了蒙山矿系列矿物的Ca端元——Ca蒙山矿及K－Ba－Ca三个端元蒙山矿在同一矿物颗粒中的共存现象；③进行了高分辨透射电镜工作，拍摄了晶格条纹象，从而完善了蒙山矿的晶体结构资料；④确定了蒙山矿后期熔融交代形成的多种矿物相。这些研究成果，证实了地幔交代作用的存在和复杂性，应引起矿物岩石学界的充分重视。     

结构矿物学的新成果(续)

含大阳离子的最紧密堆积这几年,在研究金伯利岩中副矿物(尤其是金属副矿物)时,发现有些氧化物中含有大阳离子,如K、Ca、Ba、TR等,这些矿物的特点与磁铁矿、钛铁矿很类似,结构也与最紧密堆积的矿物差不多,也可用氧的最紧密堆积原理进行解释.我们实验室与其它同行合作,发现了一个新矿物,名沂濛矿K(Cr,Ti,Fe)_(12)O_(19),太阳离子K数量很少,但起一定的晶体化学作用.因此,这几年对这个问题进行了研究.与之有关的是在研究四川攀枝花铁矿时,发现磁铁矿、甚至于钛铁矿、钒钛磁铁矿等黑色的矿物中含有Ca,Na,数量不多,但     

上地幔交代氧化物及其相关矿物──金伯利岩中复杂氧化物的相互关系及地幔交代作用探讨

用微束分析和微区图像分析技术,研究了山东金伯利岩中沂蒙矿（系列）、蒙山矿（系列）、桂红石、Zr－REE－Ti氧化物、钛铁矿（富镁）、钙钛矿和亚铁板钛矿的成分、产出特征和相互关系。这些关系包括：①镁钛铁矿-尖晶石的固溶体分离及伴生的交代作用──沂蒙矿的形成;②蒙山矿的熔融交代作用及其形成的亚铁板钛矿;③斑点、微脉交代充填作用及其形成的柱红石、Zr－REE－Ti氧化物等新矿物相。通过研究,总结了上地幔中与氧化物矿物相关的一些显交代作用的规律,提出了上地幔中不相容元素的显交代作用可分为早、中、晚三期。这些为地幔流体交代作用的总成分目录和机理作出了重要的补充。     

蒙山矿的晶体结构

本文对产于我国山东的新矿物蒙山矿(Mathiasite)进行了晶体结构精测。蒙山矿的晶体化学式为:(K、Ca、Sr)(Ti、cr、Fe、Mg、Zr)_(21)O_(38),三方晶系,空间群R,晶胞参数:a_o=10.3722,c_o=20.7161(六方定向),a_R=9.1403,a=69.187°(菱面体定向)。应用RASA-5RP自动转靶四圆单晶衍射仪,对蒙山矿收集了独立的1554个衍射强度。经结构解析和修正,求得了晶体中各原子的坐标、温度因子、占位度。并计算了原子的间距和键角。结构修正的偏离因子: R=0.047。蒙山矿产于金伯利岩中,形成于高温高压下。通过结构测定,确定了该矿物中Ti、Cr、Mg、K等元素的配位形式,特别是查明了Zr在这种以Ti为主的复杂氧化物中有独立的结晶学位置,并有缺席现象。以上研究成果丰富了金伯利岩中金属副矿物的矿物学和晶体化学内容。     

Mg-Cr~(2+)橄揽石、辉石和尖晶石的晶胞参数测定及Cr~(2+)在各晶体结构中的占位

本文用Mg－Cr2+做榄石、辉石、尖晶石的粉晶X射线衍射数据，采取“整体图谱最小二乘Rietveld”方法计算了上述矿物的晶胞参数和摩尔体积，并对Cr2+在各晶体结构中的占位情况进行了研究。结果显示，各矿物的晶胞参数随含Cr2+量的增大而增大。据Vegard定律，推算出各端元组分铬橄榄石（Cr2SiO1）、铬辉石（Cr2SiO2O6）及立方铬尖晶石（Cr3O4）的摩尔体积分别为47．7，68．0，44．9cm3。精化结构参数指示，在橄榄石中，Cr2+随机分配在两个八面体（M1，M2）位置；在辉石中，Cr2+优先选择八面体M2位置；在尖晶石中，Cr2+占置四面体位置。这种晶体内离子分配可从离子半径差别或晶体场稳定能大小得到解释。     

从上地幔相关的交代钛氧化物矿物研究看中国及南非金伯利岩地球化学性质的相似性

通过对山东蒙阴金伯利岩中富含硅酸盐不相容元素的锶钛铁矿族（ＬＩＭＡ系列）、磁铁铅矿族（ＨＡＹＩ系列）矿物及其相关的钛氧化物矿物的探针成分分析，对比南非Ｄｅｂｅｅｒｓ，Ｊａｇｅｒｓｆｏｎｔｅｉｎ及Ｂｕｌｔｆｏｎｔｅｉｎ等地金伯利岩区的相似矿物研究，发现这类矿物的产出、相互关系及化学成分非常相近，与共生的金云母、碱性闪石等含水矿物一起，反映了富Ｋ，Ｂａ，Ｔｉ，Ｚｒ，Ｎｂ，ＲＥＥ等不相容元素的流体对先前亏损的方辉橄榄岩的交代作用．ＬＩ－ＭＡ，ＨＡＹＩ系列矿物是流体对镁钛铁矿、铬尖晶石等的继承交代产物．不相容元素的局部富集还可形成一些罕见的矿物相，如ＲＥＥ－Ｔｉ及Ｚｒ－Ｔｉ氧化物．与之相关的呈海绵边或基质、空洞充填产出的钙钛矿、富锰钛铁矿、富锰锌尖晶石、柱红石、铬阿玛科矿等，则与碳酸盐化及金伯利岩岩浆晚期不相容元素的浓聚有关．对这类矿物化学成分及相互关系的研究，不但从微观角度揭示了不相容元素在部分上地幔岩石中的富集，提供了卷入交代流体的总成分目录，而且表明南非和山东金伯利岩地球化学性质的相似性     

星叶石族矿物的晶体化学

星叶石是碱性岩中分布较广泛的副矿物,成分富含碱金属K、Na及Ti,随其产出的地球化学条件,类质同象代换情况较复杂,形成许多成分异种。本工作之前对其组成和性质都不十分清楚,前人虽进行了一般矿物学研究,但未能确定所属晶系,B.C.索波列夫曾推断星叶石中Ti呈四面体配位,并与硅氧四面体组成复杂构造。     

Syngenetic inclusions of yimengite in diamond from Sese kimberlite (Zimbabwe) — evidence for metasomatic conditions of growth

Syngenetic inclusions of yimengite K (Cr, Ti, Mg, Fe, Al)₁₂O₁₉, a potassium member of the magnetoplumbite mineral group, have been recorded in an octahedral macrodiamond from the Sese kimberlite (50 km south of Masvingo, Zimbabwe). One yimengite inclusion carries lamellae of chromite suggesting peridotitic diamond paragenesis. The diamond and inclusions were studied in situ in a plate polished parallel to (011). Cathodoluminescence (CL) imaging has shown blue colour and octahedral zonation of the diamond, lack of cracks and the location of five yimengites in different growth zones. Nitrogen (N) contents (at. ppm) in the diamond determined by Fourier transform infrared spectroscopy (FTIR) steadily decrease from 576 (core) to 146 (rim). N aggregation (%1aB) is correspondingly 40% in the core and 30% in the rim. Hydrogen (H) content is high in the core, moderate in the intermediate and very high in the rim zones. Four yimengites were dated using the laser ⁴⁰Ar/³⁹Ar method. Three inclusions yielded total gas ages that agree with, or are younger than, or within error of, the Sese kimberlite eruption age (538±11 Ma) but may be compromised by gas loss. One inclusion, with the highest tapped interface gas yield, gave a total gas age of 892±21 Ma that is a likely minimum yimengite age. Time–T °C constraints from N aggregation systematics give a range of possible ages from kimberlite eruption date back to Archean and do not resolve the variable results of the ⁴⁰Ar/³⁹Ar dating. Compared with the published chemistry of yimengite from kimberlites, inclusions from the Sese diamond contain higher Al, Mg, and Sr and have lower concentration of Fe³⁺. The chondrite-normalised REE pattern of the yimengite shows enrichment in LREE and depletion in HREE, but LREE/HREE fractionations are lower than for lindsleyite–mathiasite series mantle titanates and rather similar to the REE concentrations in kimberlite and lamproite rocks. It is suggested that Sese yimengite formed in the lithospheric mantle from metasomatism of chrome spinel by a fluid rich in Ti, K, Ba and LREE.     

High-pressure synthesis of priderite and members of the lindsleyite-mathiasite and hawthorneite-yimengite series

Experiments investigating simplified members of the alkali-titanate mineral series priderite, lindsleyite-mathiasite (LIMA) and hawthorneite-yimengite (HAWYIM) confirm their stability at pressures between 3.5 and 5 GPa for priderite and LIMA, 4.3 and 5 GPa for HAWYIM at likely mantle solidus temperatures. Starting materials with K/Ba=1 resulted in solid-solutions for LIMA, whereas HAWYIM produced separate hawthorneite (K/Ba approx. 0.5) and nearly pure yimengite (K), indicating the existence of an asymmetric solvus for HAWYIM at high pressures. Priderite was examined with iron present as either Fe³⁺ or Fe²⁺; both are stable at 5 GPa, confirming the possible coexistence of priderite with diamond. X-ray powder diffraction data on end-members synthesized at high pressures and calculated reflection patterns improve the scope of diffraction data on these rare mantle minerals, with only small differences existing between the patterns for the synthetic minerals and those observed or expected for natural minerals.     

Synthesis and X-Ray Diffraction Study of All Rare-Earth Series Oxides REE_2Ti_2O_7

The pyrochlore supergroup natural minerals are the oxides for formula A2-xB2O7. In this formula, A typically is Ca, Na, TR, Ba, Fe and Mn cation. B is Ta, Ti, Nb, W, Sb. The pyrochlore supergroup is divided into five groups basis of the atomic proportions of the B-site atoms Nb, Ta, Sb, Ti, and W. They are pyrochlore, microlite, roméite, betafite, and elsmoreite, respectively. Some of these minerals containing rare-earth elements species or synthetic oxides have important applications in materials, as for optical materials, light catalyst materials, magnetoelectric materials and radioactive waste treatment etc.     

Geochemistry of an oceanite-ankaramite-basalt suite from East Island,Crozet Archipelago

The petrology and geochemistry of East Island have been investigated for the first time. The island is a deeply dissected remnant of a Pleistocene shield volcano, one of several emerging from an oceanic rise forming part of the southwest branch of the Indian Ocean ridge system. The lavas form a flat-lying sequence of oceanites, ankaramites, olivine basalts and feldsparphyric basalts, the ankaramites containing 1 cm phenocrysts of diopsidic clinopyroxene. X-Ray fluorescence analyses were made of 43 lavas for the major elements plus Cr, Ni, Rb, Sr, Ba, Pb, and Th and the minerals were analysed by electron microprobe. The elements Mg, Cr, and Ni are strongly concentrated in spinel, olivine and clinopyroxene phases and in the ankaramites and oceanite lavas with maximum concentrations of 18% MgO, 1,000 ppm Cr, 380 ppm Ni, while Al, Ti, K, Rb, Ba, Th, Na, P, Sr concentrate in the groundmass and in the feldspathic and aphyric basalts. The elements Si, Ca, Fe and Mn remain virtually constant throughout the series.Correlations of +0.95 or better exist between the concentrations of elements within the two groups given above, and negative correlations between elements in different groups. The fractionation trends are unique with respect to the constant Al/Ti ratio and K/Sr ratio, but all trends may be reproduced by calculating the effect of subtraction of suitable amounts of chromite, olivine and low Ti clinopyroxene from an alkaline olivine basalt parent. Either fractionation has taken place involving these three phases under low pressure conditions or it is the result of different degrees of partial melting of mantle material.A complex magnesian chrome spinel is found in the ankaramites and is often jacketed by a chromian titanomagnetite. A complete series of intermediate compositions appears to exist between the two end members.     

Composition and Assemblage Characteristics of Magnetic Minerals in Layer S_(5-1) of Xifeng and Duanjiapo Sections

Magneticmineralsintheloess paleosolseriesaccountforabout 1 % -2 %ofthetotal (LiuTungshengandZhangZhonghu ,1 962 ) .Duetotheiraerolianorigin ,themagneticmineralsarecomplicatedincomposition ,largeingrainsizerange ,andsignificantlydifferentincrystallinity .Asaresult,researchonthesemagneticmineralswouldbesetwithalotofdifficulties.Previousre searchersemployedopticalmicroscopic ,X raydiffractionandM ssbauerspectrometrictechniquestostudythemagneticmineralsintheloess paleosolseries,andchieflyontheb…     

Phase Relations and Stability of Magnetoplumbite- and Crichtonite-Series Phases under Upper-Mantle P-T Conditions: an Experimental Study to 15 GPa with Implications for LILE Metasomatism in the Lithospheric Mantle

High-pressure–high-temperature experiments were performedin the range 7–15 GPa and 1300–1600°C to investigatethe stability and phase relations of the K- and Ba-dominantmembers of the crichtonite and magnetoplumbite series of phasesin simplified bulk compositions in the systems TiO₂–ZrO₂–Cr₂O₃–Fe₂O₃–BaO–K₂Oand TiO₂–Cr₂O₃–Fe₂O₃–BaO–K₂O. Both seriesof phases occur as inclusions in diamond and/or as constituentsof metasomatized peridotite mantle xenoliths sampled by kimberlitesor alkaline lamprophyres. They can accommodate large ion lithophileelements (LILE) and high field strength elements (HFSE) on awt % level and, hence, can critically influence the LILE andHFSE budget of a metasomatized peridotite even if present onlyin trace amounts. The Ba and K end-members of the crichtoniteseries, lindsleyite and mathiasite, are stable to 11 GPa and1500–1600°C. Between 11 and 12 GPa, lindsleyite breaksdown to form two Ba–Cr-titanates of unknown structurethat persist to at least 13 GPa. The high-pressure breakdownproduct of mathiasite is a K–Cr-titanate with an idealizedformula KM₇O₁₂, where M = Ti, Cr, Mg, Fe. This phase possessesspace group P6₃/m with a = 9·175(2) Å, c = 2·879(1)Å, V = 209·9(1) ų. Towards high temperatures,lindsleyite persists to 1600°C, whereas mathiasite breaksdown between 1500 and 1600°C to form a number of complexTi–Cr-oxides. Ba and K end-members of the magnetoplumbiteseries, hawthorneite and yimengite, are stable in runs at 7,10 and 15 GPa between 1300 and 1400°C coexisting with anumber of Ti–Cr-oxides. Molar mixtures (1:1) of lindsleyite–mathiasiteand hawthorneite–yimengite were studied at 7–10GPa and 1300–1400°C, and 9–15 GPa and 1150–1400°C,respectively. In the system lindsleyite–mathiasite, onehomogeneous Ba–K phase is stable, which shows a systematicincrease in the K/(K + Ba) ratio with increasing pressure. Inthe system hawthorneite–yimengite, two coexisting Ba–Kphases appear, which are Ba rich and Ba poor, respectively.The data obtained from this study suggest that Ba- and K-dominantmembers of the crichtonite and magnetoplumbite series of phasesare potentially stable not only throughout the entire subcontinentallithosphere but also under conditions of an average present-daymantle adiabat in the underlying asthenosphere to a depth ofup to 450 km. At still higher pressures, both K and Ba may remainstored in alkali titanates that would also be eminently suitablefor the transport of other ions with large ionic radii. KEY WORDS: crichtonite; magnetoplumbite; high-P–T experiments; phase relations; upper mantle     

粘土矿物分子片段Si_6O_(18)H_(12)、(Si_5AlO_(18)H_(12))~-和(Si_4Al_2O_(18)H_(12))~(2-)的计算研究

采用最新的量子化学半经验计算方法MNDO－PM3，对作为粘土矿物结构基元的六元环分子体系进行了结构与能量的计算，揭示了结构变形的精确程度，并利用能量的差异大小，讨论了几种同分异构体的稳定性。