共生于同一金刚石中的超镁铁岩与榴辉岩矿物包裹体

辽南５０号金伯利管金刚石的包裹体类型一直被认为是以超镁铁岩组合为主。最近，在同一岩管中发现颗金刚石中有两种组合类型矿物共生：橄榄石，为超镁铁岩型；石榴石，绿辉石，为榴辉岩型组合。化学成分分析还表明，同一矿物的不同颗粒化学成分没有明显变化。     

沅江辰溪地区河流碎屑石榴子石地球化学特征及其对湖南原生金刚石找矿的启示

湖南沅江是我国砂矿金刚石的重要产地,石榴子石和金刚石是砂矿中常见的重矿物,与金刚石相关的石榴子石特征研究,对揭示湖南砂矿金刚石的来源与形成条件有重要意义。本文随机选取湖南沅江辰溪地区金刚石砂矿中160粒碎屑石榴子石和5粒金刚石包裹体中的石榴子石,采用矿物学、地球化学并借鉴统计学方法对它们进行了分析比较。结果显示,碎屑石榴子石主要为铁铝-锰铝榴石系列,其中个别石榴子石含有金刚石包裹体。聚类分析、线性判别、逻辑回归分析计算显示,部分G3榴辉岩型石榴子石与金刚石可能具有成生联系。同时,两个采集地点的石榴子石类型、主微量元素具有一定的差异,其中一个地点的石榴子石样品DJZ-7-1具有与金刚石更强的亲缘性。基于本文碎屑石榴子石Si值大于3.02以及前人对湖南金刚石限定的温压条件进行分析,认为湖南金刚石可能形成于深度小于220 km的橄榄岩-榴辉岩混杂区,该区域系钾镁煌斑岩型金刚石来源的优势区域。据此,建议可在辰溪赤岩村河段上游区域进一步寻找幔源G3型石榴子石以及钾镁煌斑岩,以期发现原生金刚石矿床。     

湖南砂矿金刚石包裹体原位测试:对金刚石成因来源的启示

包裹体是探究矿物结晶生长过程及其地球化学环境的重要探针,是反演寄主矿物形成机制及形成环境的有效工具。本文采用显微激光拉曼光谱、电子探针和LA-ICP-MS技术对来自湖南沅水流域的24颗宝石级金刚石的包裹体进行了原位分析。结果显示,湖南砂矿金刚石中橄榄岩型和榴辉岩型包裹体比例接近,橄榄岩型和榴辉岩型包裹体可在同一颗金刚石中"共存";湖南金刚石形成时地幔的温度和压力分别为1109~1237℃和4.05~5.83 GPa,相应的形成深度大致为133~192 km;包裹体成分及组合特征显示,扬子克拉通金刚石的形成环境与华北克拉通金刚石有显著差异,前者的形成与榴辉岩的关系更为密切,暗示有古老的地壳物质参与了金刚石的形成过程。     

大别造山带超高压变质岩折返隆升的地层学证据—毛坦厂组榴辉岩砾石的启示

大别山北缘地区发育厚达近万米的中新生代碎屑岩，它们记录着大别山造山带和在株罗纪以来的演化历史。在安徽省六安地区毛坦厂组中，发现多块榴辉岩砾石。砾石新鲜，质地坚硬，表明属于第一旋回砾石。榴辉岩由石榴子石、多硅白云母、绿帘石、石英、金红石等组成。具有明显的退变质作用，发育以钠长石和闪石类组成的后合成晶、以及石榴子石周边的次为边。石榴子石以铁铝榴石和钙铝榴石为主，恪地C类榴辉岩。根据其特征应该属于大别山南部和北部超高压榴辉岩。毛坦厂组层位确切，古生物化石和同位素年龄都表明以晚株罗世为主，这一发现表明，在晚株罗世，以榴辉岩为代表的造山带根部物质，即：超高压变质岩已经出露地表，并作为毛坦厂组的物源。因此，大别造山带超高压为质岩折返到地表，最迟在晚株罗世。     

基于红外光谱-拉曼光谱研究山东郯城砂矿的金刚石及包裹体类型

对山东郯城砂矿中的金刚石开展了傅里叶红外光谱和显微激光拉曼光谱的测试,结果显示,红外光谱均可见C—C的本征峰;绝大多数可见氮的吸收峰:双氮的吸收峰、聚合氮的吸收峰和氮片晶的吸收峰;部分可见氢的吸收峰:C—H的吸收峰、C—N的吸收峰和H2O的吸收峰.郯城金刚石以Ⅰa型金刚石为主,有ⅠaA、ⅠaB、ⅠaAB型,而Ⅱa型仅1粒;氮类型包括双氮(A心)、聚合氮(B心)及氮片晶(B'心),说明金刚石中的孤氮(C心)已经转化为双原子氮,但部分双原子氮未完成进一步的聚形.金刚石拉曼峰值集中在1131 cm–1,拉曼位移漂移程度较小,说明金刚石内部应力发生小幅的变化.在郯城金刚石中首次发现柯石英包裹体,出现139 cm–1、152 cm–1、212 cm–1、272 cm–1、328 cm–1、356 cm–1、428 cm–1和529 cm–1左右的拉曼峰值.在1粒金刚石中柯石英包裹体数量多达十余个,直径几μm至几十μm,呈针状、哑铃状、浑圆状和短柱状等多种形态.郯城金刚石中柯石英包裹体的出现,可作为郯城地区存在榴辉岩型金刚石的可靠标志,也佐证了该地部分金刚石的来源可能和洋壳循环或者俯冲过程有关.镁橄榄石包裹体上覆分散的黑色石墨斑点,与山东蒙阴、辽宁和湖南金刚石中的镁橄榄石等不同种类包裹体具有相似特征,推测这些石墨斑点是晶体包裹体形成后,由于外部环境温压条件的变化产生.     

柴北缘鱼卡榴辉岩型金红石矿床成矿物理条件

鱼卡榴辉岩型金红石矿床位于柴北缘超高压变质带西侧,是青藏高原发现的第一个超大型金红石矿床。为研究该矿床的控矿因素和成矿机制,在详细的野外地质调查和岩相学研究的基础上,利用电子探针对该矿床榴辉岩中的各特征矿物进行分析。研究表明,粗粒块状高钛榴辉岩的石榴子石保存了较完整的成分环带,从核部到边部,石榴子石的化学成分、矿物包裹体的种类和粒度都具有明显的分带性;细粒片麻状低钛榴辉岩的矿物颗粒较小,石榴子石的成分环带较差。鱼卡榴辉岩的p-T演化特征反映,它们经历了深俯冲阶段的升温升压到早期折返阶段的升温降压,再到之后的降温降压的顺时针演化轨迹。榴辉岩中进变质矿物组合和生长环带的保存说明,榴辉岩的形成经历了相对快速俯冲和折返的动力学过程,钛成矿作用时金红石很少发生转变。超高压变质前后为金红石最主要的成矿期。     

大别山超高压岩石的流变学研究

本文利用野外构造解析、透射电镜、岩组等手段,对大别山地区超高压岩石的变形表象及变形机制进行了详细的观察和研究,从而动态地建立了超高压岩石折返的PTtD轨迹。结果表明:超高压石榴橄榄岩经历了高温和低温两种变形,其中橄榄石中发育高温[001](100)和中低温[010](100)两种滑移系。超高压榴辉岩中绿辉石的位错构造发育,位错密度为4.98×10~7/cm~2。绿辉石亚颗粒的特征显示存在颗粒边界迁移和扩散蠕变。绿辉石的组构测定表明,绿辉石晶内塑性流动形成了[001]极密,该极密平行于线理,属L型收缩组构。组构对称型显示本区榴辉岩以共轴变形为主,由于应变分解,部分地区含非共轴成分。付林图解表明,绿辉石和石榴子石的变形均属于收缩型椭球,拉伸型应变,这与绿辉石组构测定结果一致。石榴子石位错密度为3.54×10~7/cm~2,部分地区的石榴子石发育动态重结晶及核幔构造等,形成榴辉岩相糜棱岩。另外根据不同超高压岩石中石英的位错密度或亚颗粒大小,计算了超高压岩石折返时各个阶段的应力大小。     

大别—苏鲁超高压榴辉岩中高钛石榴子石的成分特征及其与金红石包裹体的成因联系

石榴子石是榴辉岩中的基本造岩矿物。本文对苏鲁地体中的毛北榴辉岩和大别地体中的双河榴辉岩中的石榴子石进行了研究。结果显示,石榴子石都表现出中心“富”钛特征,即石榴子石颗粒的中心部位的TiO₂含量（0.10%~0.50%）明显高于正常榴辉岩中石榴子石的钛含量(TiO₂ 一般<0.1%)。另外,在石榴子石中心部位含有大量金红石及其它钛矿物包裹体,其定向分布特征揭示其出溶成因模式。计算结果显示,出溶金红石的原始石榴子石大约含1.7% TiO₂,揭示其超深源特征。此外,在石榴子石中发现了一颗TiO₂含量达8%~9%的钙铝榴石,具超深源成因特征。因此,本文认为超钛钙铝榴石也是超高压变质作用的标志矿物。     

大别山北部榴辉岩的退变质特征及其地质意义

研究了大别山北部榴辉岩的变质岩岩石学。结果表明，该区榴辉岩相变质作用可分为早期(超高压)和晚期(高压)两个阶段，并在折返过程中形成了一系列特征性的退变质显微构造。其中，退变质结构主要包括：(1)由于压力降低而出溶形成的一些定向针状或叶片状矿物包裹体，如钠质单斜辉石中石英及石榴子石中的金红石、单斜辉石和磷灰石等；(2)冠状体或后成合晶，特别是石榴子石外围发育两期(“双层”)后成合晶；(3)反应边或退变边，如绿辉石的透辉石退变边、透辉石的角闪石退变边和金红石的钛铁矿退变边等。这些退变质结构为本区榴辉岩高级变质岩的快速折返过程和抬升历史提供了强有力的岩石学依据；石榴子石中针状矿物出溶体进一步证明研究区榴辉岩早期经历了超高压变质作用，峰期变质压力应大干4．0GPa，甚至可能达到5～7GPa或更高。     

榴辉岩中石榴子石—单斜辉石地质温度计

通过对大别山双河榴辉岩的实例研究,对石榴子石-单斜辉石地质温度计的应用性和计算方法进行了讨论。与其他地质温度计（如氧同位素温度计）相比较,结合动力学研究,有助于进一步深入了解石榴子石-单斜辉石温度计的应用。该温度计能够较为准确地反映榴辉岩的顶峰变质温度,并且使恢复岩石体系的冷却历史成为可能。     

Roles of xenomelts,xenoliths, xenocrysts,xenovolatiles, residues,and skarns in the genesis,transport, and localization of magmatic Fe-Ni-Cu-PGE sulfides and chromite

Most sulfide-rich magmatic Ni-Cu-(PGE) deposits form in dynamic magmatic systems by partial melting S-bearing wall rocks with variable degrees of assimilation of miscible silicate and volatile components, and generation of barren to weakly-mineralized immiscible Fe sulfide xenomelts into which Ni-Cu-Co-PGE partition from the magma. Some exceptionally-thick magmatic Cr deposits may form by partial melting oxide-bearing wall rocks with variable degrees of assimilation of the miscible silicate and volatile components, and generation of barren Fe ± Ti oxide xenocrysts into which Cr-Mg-V ± Ti partition from the magma. The products of these processes are variably preserved as skarns, residues, xenoliths, xenocrysts, xenomelts, and xenovolatiles, which play important to critical roles in ore genesis, transport, localization, and/or modification. Incorporation of barren xenoliths/autoliths may induce small amounts of sulfide/chromite to segregate, but incorporation of sulfide xenomelts or oxide xenocrysts with dynamic upgrading of metal tenors (PGE > Cu > Ni > Co and Cr > V > Ti, respectively) is required to make significant ore deposits. Silicate xenomelts are only rarely preserved, but will be variably depleted in chalcophile and ferrous metals. Less dense felsic xenoliths may aid upward sulfide transport by increasing the effective viscosity and decreasing the bulk density of the magma. Denser mafic or metamorphosed xenoliths may also increase the effective viscosity of the magma, but may aid downward sulfide transport by increasing the bulk density of the magma. Sulfide wets olivine, so olivine xenocrysts may act as filter beds to collect advected finely dispersed sulfide droplets, but other silicates and xenoliths may not be wetted by sulfides. Xenovolatiles may retard settling of – or in some cases float – dense sulfide droplets. Reactions of sulfide melts with felsic country rocks may generate Fe-rich skarns that may allow sulfide melts to fractionate to more extreme Cu-Ni-rich compositions. Xenoliths, xenocrysts, xenomelts, and xenovolatiles are more likely to be preserved in cooler basaltic magmas than in hotter komatiitic magmas, and are more likely to be preserved in less dynamic (less turbulent) systems/domain/phases than in more dynamic (more turbulent) systems/domains/phases. Massive to semi-massive Ni-Cu-PGE and Cr mineralization and xenoliths are often localized within footwall embayments, dilations/jogs in dikes, throats of magma conduits, and the horizontal segments of dike-chonolith and dike-sill complexes, which represent fluid dynamic traps for both ascending and descending sulfides/oxides. If skarns, residues, xenoliths, xenocrysts, xenomelts, and/or xenovolatiles are present, they provide important constraints on ore genesis and they are valuable exploration indicators, but they must be included in elemental and isotopic mass balance calculations.     

深部矿井水煤共采水文地质数值分析

针对兖州煤田下组煤深部开采受奥灰高承压水威胁以及当地大型煤化工企业生产用水量大的现状,在已进行的水文地质勘探及放水试验基础上,评价奥灰富水性,并采用有限差分法进行奥灰疏水降压数值模拟研究,提出水煤共采观点。研究结果表明:兖州煤田深部奥灰水压高,合理布置水煤共采孔,可以实现奥灰水位的有效疏降,疏降中心区水位最大降深可达110 m,突水系数显著下降,提高了下组煤开采的安全性;同时可提供煤化工43200 m3/d的供水量,能达到可持续的、水资源保护性的供水效果,实现下组煤的水煤共采。     

Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

Partition coefficients of Hf,Zr, and REE between zircon,apatite, and liquid

Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10–100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite.     

Distribution of Cu,Co, As,and Fe in mine waste,sediment, soil,and water in and around mineral deposits and mines of the Idaho Cobalt Belt,USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

Partitioning of Hf,Lu, Ti,and Mn between olivine,clinopyroxene and basaltic liquid

The crystal/liquid partition coefficients of Lu, Hf, Ti, Mn and Ca have been measured between olivine, clinopyroxene and basaltic melt. The Ti, Mn, and Ca partition coefficients were determined at natural abundance levels. The Lu and Hf partition coefficients were determined at doping levels ranging from 0.5 to 1.5 wt% “trace element” as oxide in order to allow analysis by electron microprobe. Olivine/liquid partition coefficients for Lu, Hf, Ti, Mn, and Ca were determined at 1 bar and temperatures from 1150 to 1177° C. Clinopyroxene/liquid partition coefficients were determined for Lu, Hf, Ti, and Mn at pressures of 10, 15, and 20 kbars and temperatures from 1250 to 1290° C. The olivine/liquid partition coefficients of Hf, Lu, Ti, and Ca are small. D(Hf-ol) is zero within the analytical uncertainty. Both D(Lu-ol) and D(Mn-ol) decrease with increasing temperature, but D(Ti-ol) and D(Ca-ol) are constant over the narrow temperature range studied. The partition coefficient results are summarized below.

Distribution of copper,cobalt and nickel in ores and host-rocks,Ingladhal, Karnataka,India

Stratiform quartz-sulphide lodes in Ingladhal occur in a typical Precambrian green-stone-belt environment comprising metabasalts, tuff, chert and cherty iron-sulphide formation. Unusually high cobalt contents of metavolcanics and of sulphide minerals in orebodies suggest a consanguinity between ores and rocks. 90% of total nickel, 70% of total cobalt but only 30% of total copper in rocks occur in silicate phases and thus indicate an early separation of copper from cobalt and nickel. Unusually high non-sulphide copper in barren bedded cherts implies availability of Cu-rich solution prior to their lithification. Pyrite in sediments, in volcanics, and in orebodies is characterized by a distinctive pattern of Co-Ni distribution in each case. Partitioning of Co and Ni between coexisting sulphide pairs is complex, but gross equilibrium is indicated. Very high trace metal content of orebody pyrite sharply contrasts with very low such values in pyrite from adjacent sediments and points to a higher temperature of formation of orebodies.