阜新中生代火山岩的铂族元素特征——以碱锅和乌拉哈达为例

采用镍锍火试金法结合ICP—MS分析了碱锅玄武岩和乌拉哈达高镁安山岩样品中的Ir．Ru、Rh、Pt和Pd的含量。原始地幔标准化后的PGE分布模式呈正斜率型，Pd／Ir值高于相应的地幔比值，表明铂族元素发生了分异，这是由于在部分熔融过程中，Ir存在于地幔矿物相尖晶石和合金中，而Pd赋存于硫化物中造成的，乌拉哈达高镁安山岩中的铂族元素还可能在结晶分异过程中受到先期结晶的矿物相和合金的影响。阜新火山岩Pt的负异常可能是包含Pt的金属合金残留在地幔中造成。     

华北北缘大同地区三叠纪煌斑岩铂族元素成因研究

华北克拉通北缘中段大同地区发育呈岩墙形式产出的煌斑岩,该煌斑岩为超钾质碱性岩,极度低硅低钠高镁高钙高钾,且富H_2O和CO_2等流体组分。本文利用镍锍试金-电感耦合等离子体质谱法测定了这套煌斑岩的铂族元素组成,获得了其形成及演化过程的一些信息。大同煌斑岩铂族元素含量极低,∑PGE=2.14×10~(-9)~4.50×10~(-9),原始地幔标准化铂族元素配分型式为左倾型,亏损Ir亚组(IPGE),富集Pd亚组(PPGE),(Pd/Ir)_N=3.48~10.43。低铂族元素含量、高Cu/Ni比值(48101~90926)和高(Pd/Ir)_N比值指示大同煌斑岩形成于地幔低程度部分熔融(1%~13%),熔体形成时仍有部分硫化物残留于源区。岩浆演化过程中,未发生明显的结晶分异作用和地壳混染作用,硫未达到饱和-过饱和,未发生硫化物熔离作用。计算获得铂族元素在原始地幔与煌斑岩熔体间的分配系数分别为D_(Os)=35~124,D_(Ir)=13~35,D_(Ru)=34~91,D_(Rh)=5.8~10,D_(Pt)=3.1~9.7,D_(Pd)=2.2~4.5;PPGE较IPGE明显更不相容。与峨眉山大火成岩省玄武岩对比研究发现,岩浆岩中的铂族元素含量主要受源区地幔部分熔融程度和演化过程中硫化物熔离作用共同影响;而铂族元素之间的分异受源区部分熔融程度和岩浆分离结晶作用共同影响。     

大别造山带毛屋超镁铁岩的铂族元素研究

采用镍锍火试金法结合ICP-MS分析了毛屋斜方辉石岩和石榴二辉岩样品中的Ir、Ru、Rh、Pt和Pd的含量,结果显示其铂族元素(PGE)的含量随岩石类型无规律性的变化,原始地幔标准化后的铂族元素分布模式呈负斜率,Pd、Ir发生了分异。毛屋超镁铁岩铂族元素特征的形成受岩石中铂族元素的存在相制约,PPGE富集在富Cu硫化物,而IPGE以类似残留相、不熔的单硫化物固熔体形式存在,其中地壳混染也起了一定的作用;同时,成岩过程中流体的存在造成了Pt和Pd的活化。因此,单硫化物固熔体和流体的共同作用形成了毛屋超镁铁岩类似残留地幔岩的铂族元素分布特征。     

黔西地区峨眉山玄武岩（东岩区）铂族元素地球化学特征

利用同位素稀释-等离子体质谱(ICP-MS)方法测定了黔西水域、威宁等地的东岩区峨眉山玄武岩的铂族元素含量。结果表明，相对于原始地幔，东岩区峨眉山玄武岩的铂族元素发生了较强的分异作用，Os、Ir、Ru、Rh亏损，Pd、Pt发生富集，相对配分模式为Pd-Pt富集型；经球粒陨石及原始地幔标准化的铂族元素配分模式为向左陡倾斜型，具有陡的正斜率，Pd／Ir显著高于原始地幔、球粒陨石、原始上地幔等，而与地幔低度熔融形成的N-MORB、大陆拉斑玄武岩等接近，表明峨眉山玄武岩的物质来源为上地幔熔融程度偏低的玄武岩浆。     

铂族元素地球化学研究评述

随着分析技术的发展和数据的积累,人们逐渐认识到PGE在地球化学研究方面具有潜在的应用价值。但地幔中PGE的存在形式目前尚不清楚,在许多方面还有争议。文中通过大量的实例综述了近年来PGE的分异机制和其在上地幔分布不均一性方面取得的进展以及存在的问题,结果表明:除Au外,蚀变作用并不影响PGE的分异;PGE主要以硫化物或合金的形式赋存于地幔岩石中,其分布不均匀,单一地依靠PGE与MgO,Cr,Ni的相关性来探讨部分熔融、分离结晶过程中橄榄石、尖晶石、铬铁矿对PGE分异的影响是不全面的,必须考虑硫化物的作用;地幔岩石具有包裹体和粒间两种不同PGE分配模式的硫化物。地幔源区或板内携带PGE流体交代以粒间硫化物为主的地幔岩石。使其PGE发生分异;不管是核幔分离后外核物质的返回,还是单一硫化物的作用都不能完全否定陨石撞击的地球增生假说。在大的区域,上地幔PGE的分布是均一的,但在一定范围内由于不同的大地构造背景,其PGE的分布显示不均一性。     

峨眉山玄武岩的铂族元素地球化学特征

采用镍锍试金预处理中子活化分析方法,系统地测定了峨眉山玄武岩的铂族元素含量。１４个样品的平均值为：Ｏｓ＝０．３９ｎｇ／ｇ,Ｉｒ＝０．０６９８ｎｇ／ｇ,Ｒｕ＝０．４９ｎｇ／ｇ,Ｒｈ＝０．２５ｎｇ／ｇ,Ｐｔ＝７．７１ｎｇ／ｇ,Ｐｄ＝５．４８ｎｇ／ｇ。相对于原始上地幔,峨眉山玄武岩的铂族元素分异明显,Ｏｓ、Ｉｒ、Ｒｕ、Ｒｈ亏损,Ｐｔ、Ｐｄ富集。（Ｐｔ＋Ｐｄ）／（Ｏｓ＋Ｉｒ＋Ｒｕ）比值（平均１３．９６）和Ｐｄ／Ｉｒ比值（平均７８．５）显著高于原始上地幔、地幔捕虏体、阿尔卑斯型橄榄岩及科马提岩。铂族元素配分模式为铂钯富集型。以上这些特征表明其原始岩浆为上地幔低程度部分熔融形成的玄武岩浆。     

新疆坡北铜镍矿床铂族元素特征及其对成矿过程的约束

坡北铜镍矿床位于塔里木克拉通东北缘,矿石类型主要为星点状和稀疏浸染状,二者之间呈渐变过渡关系。矿石∑PGE含量较低,变化范围为2.47×10-9~404.17×10-9;S与Ni之间相关性较差,与Cu、Ir、Ru、Rh、Pt、Pd之间除个别样品外均呈较好的正相关性,表明铂族元素主要赋存于硫化物中。在铂族元素相关性图解上,Ir与Ru、Rh之间呈明显的正相关性,与Pd之间相关性较差,Pd与Ru、Rh、Pt之间均呈很好的正相关性,表明硫化物熔离后未发生明显的单硫化物固溶体（MSS）的分离结晶。100%硫化物计算后,矿石∑PGE平均含量为2 806.9×10-9,原始地幔标准化图解呈Pd、Pt略富集的左倾型,相对于Ni、Cu明显亏损铂族元素。模拟计算表明坡北矿床多数样品硫化物熔离时“R”因子变化范围为50~500,母岩浆中Ru含量约为0.56×10-9,Pd含量为3.6×10-9。研究表明导致铂族元素亏损的主要原因是岩浆源区残留有少量硫化物,成矿过程中深部携带硫化物珠滴的岩浆进入现存空间时岩浆流动速度较慢,硫化物聚集过程中流动分异作用微弱,限制了硫化物的聚集,使硫化物较为分散,可能是导致该矿床金属品位较低的主要原因。     

滇西金宝山富铂钯岩体岩浆源区研究：铂族元素和Sr-Nd同位素约束

金宝山杂岩体位于扬子板块西缘,毗邻哀牢山造山带北段,岩体中蕴含丰富的铂钯资源,是峨眉山大火成岩省(ELIP)中大型岩浆型铂族元素矿床。岩体的主要组成为辉石橄榄岩,矿体以似层状、透镜状产出于辉石橄榄岩中。地幔是镍矿床和铂族元素矿床最重要的源区,因而对Ni、Cu及PGE等元素行为的研究,是剖析岩浆型Ni-Cu-PGE矿床源区特征的一个重要研究方向。该研究获得金宝山岩体中辉橄岩铂族元素及Sr-Nd同位素数据,结合前人对ELIP中不同类型岩石系列PGE成分研究及Ni、Cu、PGE等元素在岩浆和硫化物中的分配系数,半定量模拟得到金宝山原始岩浆的形成源于地幔中高度部分熔融(25%~40%)形成的富PGE岩浆(含12.8×10-9 Pd,9.8×10-9 Pt,0.6×10-9 Rh和0.7×10-9 Ir),其铂族元素成分与ELIP苦橄岩成分相当,并且岩浆在演化的过程中遭受了10%~20%地壳混染作用。利用批式部分熔融公式及各铂族元素在硅酸盐矿物和熔体之间的分配系数反演计算得到产生金宝山熔体的地幔约含有5.3×10-9 Pd,7.5×10-9 Pt,0.75×10-9 Rh和1.5×10-9 Ir,相比原始地幔而言并没有表现出明显富集PGE的特征。这表明地幔中高度部分熔融+大量岩浆与硫化物的充分反应是形成大型岩浆型铂族元素矿床的一种可具备的条件。     

内蒙古柯单山蛇绿岩地幔橄榄岩铂族元素(PGEs)的分布特征及分异机制探讨

采用Carius管结合MC-ICPMS法分析了内蒙古柯单山蛇绿岩地幔橄榄岩中Ir、Ru、 Pt 和Pd 的含量,与典型的地幔橄榄岩进行对比研究,发现柯单山地幔橄榄岩中Ir和Ru明显亏损,Pt和Pd强烈富集,具有极高的Pd/Ir值,PGEs地幔标准化配分模式具有较陡的正斜率,明显不同于通常观测到的代表部分熔融残留相中铂族元素配分模式(负斜率或平坦型)。柯单山地幔橄榄岩的Ir和Ru与MgO呈正相关关系,表明Ir和Ru的亏损可能与部分熔融过程中硫化物的消耗程度有关,而与PGEs在硫化物/硅酸盐间的能斯特分配系数没有直接关系; Pt、Pd的富集表明本区的地幔橄榄岩不仅仅是经历过部分熔融的残余,而与来自深海的橄榄岩和大陆岩石圈地幔(SCLM)中的方辉橄榄岩相似,因此推测,本区地幔橄榄岩在部分熔融后又经历了富Pd的熔/流体交代,而熔/流体的来源可能是在岩浆分异演化过程中"熔离"出来的硫化物。     

The formation of SiO<Subscript>2</Subscript>-rich melts within the deep oceanic crust by hydrous partial melting of gabbros

Small amounts of felsic, evolved plutonic rocks, often called oceanic plagiogranites, always occur as veins or small stocks within the gabbroic section of the oceanic crust. Four major models are under debate to explain the formation of these rocks: (1) late-stage differentiation of a parental MORB melt, (2) partial melting of gabbroic rocks, (3) immiscibility in an evolved tholeiitic liquid, and (4) assimilation and partial melting of previously altered dikes. Recent experimental data in hydrous MORB-type systems are used to evaluate the petrogenesis of oceanic plagiogranites within the deep oceanic crust. Experiments show that TiO₂ is a key parameter for the discrimination between different processes: TiO₂ is relatively low in melts generated by anatexis of gabbros which is a consequence of the low TiO₂ contents of the protolith, due to the depleted nature of typical cumulate gabbros formed in the oceanic crust. On the other hand, TiO₂ is relatively high in those melts generated by MORB differentiation or liquid immiscibility. Since the TiO₂ content of many oceanic plagiogranites is far below that expected in case of a generation by simple MORB differentiation or immiscibility, these rocks may be regarded as products of anatexis. This may indicate that partial melting processes triggered by water-rich fluids are more common in the deep oceanic crust than believed up to now. At slow-spreading ridges, seawater may be transported via high-temperature shear zones deeply into the crust and thus made available for melting processes.     

An experimental study on the shallow-level migmatization of ferrogabbros from the Fuerteventura Basal Complex, Canary Islands

Spectacular shallow-level migmatization of ferrogabbroic rocks occurs in a metamorphic contact aureole of a gabbroic pluton of the Tierra Mala massif (TM) on Fuerteventura (Canary Islands). In order to improve our knowledge of the low pressure melting behavior of gabbroic rocks and to constrain the conditions of migmatization of the TM gabbros, we performed partial melting experiments on a natural ferrogabbro, which is assumed as protolith of the migmatites. The experiments were performed in an internally heated pressure vessel (IHPV) at 200 MPa, 930–1150 °C at relatively oxidizing conditions. Distinct amounts of water were added to the charge.

From 930 to 1000 °C, the observed experimental phases are plagioclase (An_60–70), clinopyroxene, amphibole (titanian magnesiohastingsites), two Fe–Ti oxides, and a basaltic, K-poor melt. Above 1000 °C, amphibole is no longer stable. The first melts are very rich in normative plagioclase (>70 wt.%). This indicates that at the beginning of partial melting plagioclase is the major phase which is consumed to produce melt. In the experiments, plagioclase is stable up to high temperatures (1060 °C) showing increasing An content with temperature. This is not compatible with the natural migmatites, in which An-rich plagioclase is absent in the melanosomes, while amphibole is stable. Our results show that the partial melting of the natural rocks cannot be regarded as an “in-situ” process that occurred in a closed system. Considerable amounts of alkalis probably transported by water-rich fluids, derived from the mafic pluton underplating the TM gabbro, were necessary to drive the melting reaction out of the stability range of plagioclase. A partial melting experiment with a migmatite gabbro showing typical “in-situ” textures as starting material supports this assumption.

Crystallization experiments performed at 1000 °C on a glass of the fused ferrogabbro with different water contents added to the charge show that generally high water activities could be achieved (crystallization of amphibole), independently of the bulk water content, even in a system with very low initial bulk water content (0.3 wt.%). Increasing water contents produce plagioclase richer in An, reduces the modal proportion of plagioclase in the crystallizing assemblage and extends the melt fraction. High melt fractions of >30 wt.% could only be observed in systems with high bulk water contents (>2 wt.%). This indicates that the migmatites were generated under water-rich conditions (probably water-saturated), since those migmatites, which are characterized as “in-situ” formations, show generally high amounts of leucosomes (>30 wt.%).     

Revisiting platinum group elements of Late Permian coals from western Guizhou Province, SW China

Twenty five coal samples from the Late Permian coal-bearing strata in Weining, Nayong, and Zhijin, western Guizhou Province, SW, China, were analyzed for platinum group elements (PGEs). The coal ashes were digested by the Carius tube technique and accurately measured by isotope dilution-inductively coupled plasma mass spectrometry (ID-ICP-MS) for all PGEs. The results are much lower than the previous reported values. Our study suggested that the previously reported PGE values are incorrect and may due to the polyatomic interferences in ICP-MS measurements. In our study, samples from the Weining coalfield have the lowest PGE contents (from 0.019 Ir to 0.42 ng/g Pd), which represent the PGE background value in coal in western Guizhou province. Some of the coals have Pt and Pd contents about 20-times higher than the background value, indicating PGEs are concentrated. We also reported new and reliable PGE data and background value of coal in western Guizhou province, SW, China, and suggested to rework the PGE background values of Chinese coals.     

Composite carbonate and silicate multiphase solid inclusions in metamorphic garnet from ultrahigh‐P eclogite in the Dabie orogen

Composite multiphase solid (MS) inclusions composed of carbonate and silicate minerals have been found for the first time in metamorphic garnet from ultrahigh‐P eclogite from the Dabie orogen. These inclusions are morphologically euhedral to subhedral, and some show relatively regular shapes approaching the negative crystal shape of the host garnet. Radial fractures often occur in garnet hosting the inclusions. The inclusions are primarily composed of variable proportions of carbonate and silicate minerals such as calcite, quartz, K‐feldspar and plagioclase, with occasional occurrences of magnetite, zircon and barite. They are categorized into two groups based on the proportions of carbonate and silicate phases. Group I is carbonate‐dominated with variable proportions of silicate minerals, whereas Group II is silicate‐dominated with small proportions of carbonates. Trace element analysis by LA‐ICPMS for the two groups of MS inclusions yields remarkable differences. Group I inclusions exhibit remarkably lower REE contents than Group II inclusions, with significant LREE enrichment and large fractionation between LREE and HREE in the chondrite‐normalized REE diagram. In contrast, Group II inclusions show rather flat REE patterns with insignificant fractionation between LREE and HREE. In the primitive mantle‐normalized spidergram, Group I inclusions exhibit positive anomalies of Zr and Hf, whereas Group II inclusions show negative anomalies of Zr and Hf. Nevertheless, both groups exhibit positive anomalies of Ba, U, Pb and Sr, but negative anomalies of Nb and Ta, resembling the composition of common continental crust. Group I inclusions have higher Ba and U contents than Group II inclusions. Combined with petrological observations, the two groups of MS inclusions are interpreted as having crystallized from composite silicate and carbonate melts during continental subduction‐zone metamorphism. The differences in trace element composition between the two groups are primarily attributed to the proportions of carbonate and silicate phases in the MS inclusions. The silicate melts were derived from the breakdown of hydrous minerals such as paragonite and phengite, whereas the occurrence of carbonate melts indicates involvement of carbonate minerals in the partial melting and thus has great bearing on recycling of supracrustal carbon into the mantle. The coexistence of silicate and carbonate melts in the eclogitic garnet provides insights into the nature of hydrous melts in the subduction factory.     

云南维西大宝山铜矿PGE和微量元素地球化学特征及其成因意义

大宝山铜矿是青藏高原东南缘哀牢山-金沙江构造带西北部雪龙山成矿带中典型的浅成中低温热液型铜矿床.矿石和围岩的PGE和微量元素地球化学分析结果表明从围岩、矿化围岩到矿石:1)∑PGE、δRh逐渐增加,PPGE/IPGE、Pd/Ir、Pt/Ir和δPt逐渐降低.在铂族元素原始地幔标准化图解上,岩、矿石中Os、Ir、Ru和Pd具有相似的演化趋势,而矿石Rh正异常、Pt负异常明显不同于围岩.在δRh-Cu和∑PGE-Cu关系图上,Cu含量与8Rh和∑PGE呈明显的正相关关系,而在δPt-Cu关系图上表现为明显的负相关关系;2)稀土总量、轻/重稀土比值、δCe逐渐减小,Eu和Nb、Ta、Sr、Hf、Zr的亏损程度逐渐增大,矿石中大离子亲石元素存在不规律性的变化.这些特征揭示出大宝山铜矿矿石与围岩在PGE和微量元素地球化学特征上存在明显的差异.结合矿区内矿体呈脉状、受顺糜棱面理发育的脆韧性构造破碎带控制,围岩蚀变强度较弱、规模小和矿区内新生代同构造岩浆岩脉发育,以及主要矿石矿物δ34S值主要集中在+ 1.3‰～-5.2‰之间,部分落在-8.2‰～-12.8‰范围的特点,说明大宝山铜矿中的成矿物质主要来源于新生代岩浆期后热液,围岩的贡献很小.大宝山铜矿与矿区内新生代同构造岩浆岩脉同为雪龙山韧性剪切带隆升过程中形成的产物,岩浆分异产生的含矿流体在上升过程中与地下流体混合导致物理化学条件发生明显的改变,促使成矿物质沿构造破碎带晶出形成矿脉.     

铂族元素流体活动性

铂族元素(简称PGE)通常被认为是不活动性元素,可以用来示踪地幔源区和镁铁-超镁铁质岩浆的演化过程。然而,越来越多的野外地质证据和实验研究表明,PGE具有热液活动性,其活动性在指示岩石和矿床成因、地幔交代作用等方面具有重要意义。本文在回顾实际样品中PGE流体活动性的基础上,重点收集和整理了前人有关PGE流体活动性的实验研究和模型计算。大量地质记录显示岩浆活动常常伴随着热液事件发生,并且铂族元素的富集常与岩浆后期热液叠加作用以及大洋或盆地的热液事件有密切联系。溶解度实验结果表明,PGE在富Cl~-流体中的溶解度最高可达100n×10~(-6),而在富HS~-流体中则低几个数量级,仅有n×10~(-12)级别。高温高压实验及模拟计算显示,PGE通常以络合物形式在流体中进行迁移和富集,涉及的主要无机配位阴离子有Cl~-、HS~-、OH~-以及NH_3。这些PGE络合物或络合阴离子团的稳定性受流体的温度、氧逸度、离子浓度、pH等诸多因素的制约。其中,PGE-Cl络合物种型在PGE的浅部迁移中可能贡献最大,其稳定条件为中低温(300℃)、高盐度、高氧逸度、高Cl~-浓度、酸性的地质流体环境。而在还原、碱性、高S~(2-)浓度、相对中低温的流体条件下,PGE-HS种型则占主导。当流体环境为高温和碱性条件时,PGE-OH络合物种型则较为常见。相对其他几种络合物形式,PGE-NH_3对于PGE迁移的贡献较小,其最佳稳定条件为相对中低温、中碱性、相对低氧逸度的地质环境。最后,本文探讨了前人工作的不足以及未来亟需解决的问题。     

Characteristics of carbonatites from the northern part of the Korean Peninsula: A perspective from distribution,geology and geochemistry

The present study introduces the carbonatite in the northern part of the Korean Peninsula for the first time.Recent exploration and development of the phosphorus-bearing carbonate rocks in the area have accumulated new geological data which gave us an opportunity to study origin of the carbonate rocks.We conducted geological survey,geochemical analyses of trace elements and rare earth elements,and carbon and oxygen isotope analyses for the carbonatites from Ssangryong,Pungnyon,Yongyu and Puhung districts of the northern part of the Korean Peninsula.This research confirms that the phosphorus-bearing carbonate rocks are carbonatite originating from the mantle.The studied carbonatites are distributed at the junctions of ring and linear structures or around their margins and contain a greater amount of REEs,Y,and Sr than carbonate rocks.The carbonatites in Yongyu and Puhung area show evidence that they were formed from mantle plume generated at the lower mantle and display similar fractionation characteristics to carbonatites in Barrado Itapirapua in Brazil and Kalkfeld and Ondurakorume in Namibia.REE patterns of the carbonatites are typical of carbonatites and the carbon and oxygen isotope analyses demonstrate that the carbonatites were originated from mantle.The carbonatites from the northern part of the Korean Peninsula have a great potential for sources of REE,Y,PGE(platinum group elements),copper,and gold.     

Trace element composition of continentally subducted slab‐derived melt: insight from multiphase solid inclusions in ultrahigh‐pressure eclogite in the Dabie orogen

The ultrahigh‐pressure (UHP) eclogite in the Dabie orogen preserves petrological evidence for the existence of hydrous silicate melts that formed during continental subduction‐zone metamorphism. This is indicated by occurrence of multiphase solid (MS) inclusions in garnet that primarily consist of K‐feldspar + quartz ± epidote/allanite. All the MS inclusions are euhedral to subhedral in morphology and surrounded with radial cracks in the host garnet. Their trace element compositions were analysed by two different approaches of laser sampling. The mass budget method was used to estimate the trace element abundances of MS inclusions from their mixtures with the host garnet. The results are compared with the direct sampling of MS inclusions, providing a first‐order approximation to the trace element composition of MS inclusions. The MS inclusions exhibit consistent enrichment of LILE, Sr and Pb, but depletion of HFSE in the primitive mantle‐normalized spidergram. Such arc‐like patterns of trace element distribution are common for continental crustal rocks. The melts have variably high K, Rb and Sr abundances, suggesting that breakdown of phengite is a basic cause for partial melting of the UHP eclogite. These MS inclusions also exhibit consistently low HFSE and Y contents, suggesting partial melting of the eclogite in the stability fields of rutile and garnet. Consequently, the trace element composition of MS inclusions provides a proxy for that of hydrous silicate melts derived from dehydration melting of the UHP eclogite during continental collision.