吉林省油页岩中铂族元素的化学特征及分配规律研究

采用电感耦合等离子体发射质谱仪(ICP MS)测定了吉林省油页岩中铂族元素的含量,并对油页岩中铂族元素的化学特征、与无机组分的相关性及其分布模式等进行了分析和阐述。通过油页岩中铂族元素的含量与地壳和中国东部出露地壳中铂族元素丰度的比较表明,Rh、RuI、r等元素相对富集,其中松原油页岩中RhI、r的含量约为地壳平均值的10倍。研究区油页岩中铂族元素以Pt Pd分配模式为典型特征,一般Pt的丰度大于Pd。油页岩中铂族元素与无机组成相关分析的结果表明,油页岩中铂族元素可能呈吸附态存在于高岭石、伊利石等粘土矿物中。     

华北与黔西地区晚古生代煤层中铂族元素赋存状态及来源

运用电离耦合等离子体质谱仪(ICP-MS)对中国华北和黔西地区晚古生代煤系中54个样品的铂族元素(PGEs)进行了分析。分析结果表明,煤中铂族元素主要是通过岩浆热液活动、低温热液流体、同沉积火山灰、陆源碎屑输入和海水等诸种地质作用形成的,前3种作用是造成煤中铂族元素异常的主要原因。低含量的铂族元素(正常背景值)主要来源于硅质陆源区,煤中铂族元素的背景值为:Ru=0.005μg/g,Rh=0.014μg/g,Pd=0.181μg/g,Ir=0.001μg/g,Pt=0.037μg/g。煤中铂族元素以Pt-Pd分配模式为特征,并且Pd>Pt,Pd>>Ru、Rh、Ir,其中Pd在煤中的背景值约为地壳平均值的18倍。Pd、Pt与煤灰分呈正相关,表现出它与无机矿物的亲和性。     

黔西玄武岩铂、钯地球化学特征与存在状态

黔西玄武岩中铂族元素丰度较高，其含量变化顺序为Pt〉Pd〉Ru〉Ir〉Rh，表现为Pt、Pd富集，而Os、Ir、Ru、Rh亏损，说明在地幔熔融形成玄武岩的过程中，铂族元素已发生了明显的分异。在分析黔西玄武岩中Pt、Pd岩石载体所处的大地构造背景、含铂（族）矿床的可能类型和岩石化学特征与Pt、Pd可能存在状态的关系的基础上，研究了黔西玄武岩中Pt、Pd存在状态。结果表明，其状态分属硫化物态．金属互化物态、类质同像亲石态和吸附态，且各状态丰度值依次减少。     

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。     

中国大陆科学钻100～850 m深度岩心的贵金属地球化学

本文对CCSD超深钻中首次获得的铂族元素及金、银的地球化学特点进行了分析和研究,结果表明各类样品的铂族元素含量均偏低,100～850 m深度平均Ir小于0.1×10-9,Os小于0.3×10-9,Pd小于0.5×10-9,Pt小于0.4×10-9,Rh小于0.1×10-9,Ru小于0.4×10-9,只有个别橄榄岩样品的铂族元素含量接近于地壳丰度,但远远低于超基性岩的一般含量.这种极低的铂族元素含量,属于"负异常",表明在变质作用过程中铂族元素发生了活化转移.榴辉岩和橄榄岩的铂族元素含量都偏低,但其球粒陨石标准化配分明显具有明显不同的特点,利用铂族元素仍然可以帮助对变质岩进行分类或恢复原岩.前人在蒋庄超基性岩岩体的人工重砂中发现有铂族矿物,其中包括有铱铂矿.可见,铂族元素是可以活化转移的,其活化转移的原因还需要探讨,是在结晶分异过程中转移的、还是在折返过程中活化的、或者是在造山运动结束之后由于其他原因而造成的,尚需要深入研究.     

大别造山带祝家铺辉长岩的铂族元素特征

采用镍锍火试金法结合ICP-MS分析了祝家铺14个辉长岩样品中的Ir，Ru，Rh，Pt和Pd的含量。结果显示其PGE的含量较低，原始地幔标准化后的PGE分布模式呈正斜率型，PPGE相对原始地幔略微亏损，而IPGE强烈亏损，Pd／Ir值(22—138)远高于相应的地幔比值，表明铂族元素发生了分异。对祝家铺辉长岩的铂族元素研究表明，在其源区发生过硫化物的分异作用，地壳的混入可能促进了硫化物的饱和。祝家铺辉长岩中铂族元素的分异是因为在地幔部分熔融和岩浆演化过程中，PPGE主要受硫化物控制，而Ir则存在于非硫化物相如尖晶石、可能还有合金之中。     

贵州黑色岩系金-铂族元素地球化学特征及成因分析

为探讨贵州下寒武统黑色岩系中铂族元素物质来源及钼-镍、钒多金属形成的沉积环境与成矿作用,在钼-镍、钒多金属层及其顶底页岩、底部硅质岩中采集样品测试分析。通过对样品中金、铂族元素含量(质量分数)及其地球化学特征值研究,结果表明：黑色岩系中金及铂族元素含量显示协同变化特征;Pd富集,Ru、Ir亏损明显,Pt、Rh、Os基本持平或略有变化;样品的原始地幔标准值标准化模式配分曲线从Os、Ru、Rh、Ir、Pt到Pd大致呈“W”型,配分曲线略呈左倾,总体上呈现w(Pd)>w(Pt)>w(Os)>w(Rh)>w(Ru)>w(Ir)的变化关系;黑色岩系铂族元素来源与正常海水及海底热水喷流作用关系密切,地外来源可能性极小;黑色岩系钼-镍、钒多金属层中铂族元素的富集存在单独成矿作用或成矿作用的叠加,而且在钒多金属层内局部存在分层或条带分异。     

某岩体含铂矿石锇铱铑品位预报方程的建立

硫化铜镍矿床中伴生的铂族元素以Pt、Pd为主,Os、Ru、Ir、Rh含量通常较低,但价格比Pt、Pd昂贵得多.如何综合评价这些含量较低的伴生铂族元素是普查勘探工作应解决的问题之一.一种作法是将主金属Ni、Cu及6种铂族元素一并列入样品的基本分析项目,这样做便于储量计算,但将增加试金分析工作量,影响矿床勘探速度;另一种作法是只将Ni、Cu、Pt、Pd列入基本分析项目,其余4种伴生铂族元素仅在组合分析样品中进行测定,这样虽节省大量试金分析,却又给储量计算带来困难.本文应用一元线性回归分析方法,尝试依据若干代表性钻孔含铂矿石的基本分析数据,利用Os、Ru、Ir、Rh含量的密切相关关系建立预报方程,以期在只测定矿石中Ru含量的前提下,对Os、Ir、Rh品位进行预报,并讨论了预报的精确度和实际应用的可能性.     

铂族元素在地壳、岩石和沉积物中的分布

随着20世纪90年代铂族元素分析测试技术的突破性进展以及大量可靠的岩石和沉积物铂族元素含量分析数据的积累,引用20世纪80年代前发表的有关铂族元素的地壳丰度和岩石、沉积物中的平均含量作为衡量标准已不适宜。根据近15年来获得的大量的有关铂族元素含量的可靠数据,综合给出了铂族元素在地壳、岩石、土壤和沉积物中的丰度。这种对地壳、岩石和沉积物中铂族元素丰度值的新认识,对理论地球化学、勘查地球化学甚至铂族元素矿产勘查工作都具有重要的意义。     

煎茶岭与金川硫化镍矿床的铂族元素地球化学特征对比及其意义

采用ICP—MS方法分析了煎茶岭和金川硫化镍矿床岩石、矿石的铂族元素含量,煎茶岭岩体蛇纹岩的Cu／Pd比值低于原生地幔岩浆,说明岩浆熔离作用较弱,矿石的Pd／Ir比值较小,指示其多数矿石属于岩浆型,以岩浆成矿作用为主;而金川岩体的平均Cu／Pd比值远大于原生地幔岩浆,表明岩浆熔离作用强,矿石的Pd／Ir比值较大,体现了钯族元素矿化及成矿物质以幔源为主的特征。煎茶岭在成矿过程中有壳源物质的混染,整体上岩石、矿石铂族元素含量较低,这与岩浆熔离作用弱、铂族元素成矿作用不发育等因素有关;金川在成岩成矿过程中也有少量地壳物质的混染,但岩石、矿石铂族元素含量较高,反映了以岩浆深部熔离成矿作用为主的特征。     

The geochemistry of platinum group elements in marine oil shale—A case study from the Bilong Co oil shale,northern Tibet,China

The Bilong Co oil shale zone is located in the South Qiangtang depression. This zone, together with the Shengli River-Changshe Mountain oil shale zone in the North Qiangtang depression, northern Tibet plateau, represents the potentially largest marine oil shale resource in China. Seventeen samples including oil shale and micritic limestone were collected from the Bilong Co oil shale area to determine the concentrations, distribution patterns, occurrences and origins of platinum group elements (PGEs) in marine oil shale. The oil shale samples from the Bilong Co area exhibit very low total PGE contents ranging from 1.04 to 2.96 ng/g with a weighted mean value of 1.686 ng/g, while the micritic limestone samples from the Bilong Co area exhibit a little lower PGE value ranging from 0.413 to 1.11 ng/g. PGEs in oil shale samples are characterized by high contents in Pd (average 0.79 ng/g), Os (average 0.123 ng/g) and Pt (average 0.644 ng/g) compared with Ru (average 0.068 ng/g), Rh (average 0.033 ng/g) and Ir (average 0.026 ng/g). The highest values for individual PGEs are not uniformly distributed in the section. Clearly, the PGEs are generally enriched in the oil shale samples near the boundary between micritic limestone and oil shale.The individual PGEs in oil shale samples from the Bilong Co area exhibit various modes of occurrence. Ruthenium and Pt occur mainly in pyrite, while Pd is associated mainly with organic matter and Mg-minerals. Rhodium and Os are controlled mainly by pyrite and organic matter. Iridium is present mainly in other Fe-bearing minerals, rather than pyrite. The PGEs in the Bilong Co oil shale are mainly of seawater origin and possibly influenced by terrigenous supply.     

中国铬铁矿的铂族元素分布特征

用NiS溶解和Te沉淀方法富集铂族元素（PGE），制成镍扣，再溶解于浓HCl中，使PGE和Te一起沉淀。制备的样品溶液在ELAN－5000型电感耦合等离子质谱仪（ICP－MS）上分析PGE。中国铬铁矿矿石，包括蛇绿岩套中的豆荚状铬铁矿床、非层状侵入体铬铁矿，计13个矿床（化）样品，其PGE模式表明，主要呈RU正异常模式，个别不同模式是由母岩不同以及铂族元素矿化叠加引起的。铬铁矿的PGE模式不取决于铬铁矿的化学成分，而取决于其母岩性质以及形成温度和铂族元素的熔点。     

Geochemical characteristics of the platinum-group elements in the Abulangdang ultramafic intrusion,Sichuan Province,China

The contents of the platinum-group elements (PGEs: Os, Ir, Ru, Rh, Pt, Pd) in the Abulangdang ultramafic intrusion have been determined using ICP-MS after nickel sulfide fire assay preconcentration. Different samples show significant differences in absolute PGE abundance. They display a pronounced negative incline in mantle-normalized patterns which are characterized by strong enrichment in IPGEs (Os, Ir, Ru) and depleting to slight enrichment in PPGEs (Rh, Pt, Pd). The characteristics of PGE distribution in the Abulangdang rocks are due to the combined action of sulfide and non-sulfide (spinel/chromite or alloy or micro-granular aggregation of metals). In comparison with the mafic-ultramafic rocks which host Ni-Cu-PGE deposits in the Emeishan Large Igneous Province (ELIP), it is assumed that the Abulangdang ultramafic intrusion may be the product of early-stage magma activity in the ELIP.     

锍镍试金富集-等离子体质谱法测定西太平洋富钴结壳中的铂族元素

根据西太平洋麦哲伦海山富钴板状结壳样品的成分特征，对常规的锍镍试金配方作了改进；酌情减少捕集剂羰基镍的加入量，可显著降低铂族元素的空白值。富集后的样品，采用电感耦合等离子体质谱测定铂族元素（PGE）。其中，Ru、Rh、Pd、Ir和Pt用常规外标法测定，^175Lu作内标；Os用同位素稀释法测定。用国家一级标准物质GBW07290和GBW07291作监控分析质量的参考样，结果满足要求。     

Platinum-group element geochemistry of the Zhuqing Fe-Ti-V oxide ore-bearing mafic intrusions in western Yangtze Block,SW China: control of platinum-group elements by magnetite

Platinum-group element (PGE) geochemistry combined with elemental geochemistry and magnetite compositions are reported for the Mesoproterozoic Zhuqing Fe–Ti–V oxide ore-bearing mafic intrusions in the western Yangtze Block, SW China. All the Zhuqing gabbros display extremely low concentrations of chalcophile elements and PGEs. The oxide-rich gabbros contain relatively higher contents of Cr, Ni, Ir, Ru, Rh, and lower contents of Pt and Pd than the oxide-poor gabbros. The abundances of whole-rock concentrations of Ni, Ir, Ru, and Rh correlate well with V contents in the Zhuqing gabbros, implying that the distributions of these elements are controlled by magnetite. The fractionation between Ir–Ru–Rh and Pt–Pd in the Zhuqing gabbros is mainly attributed to fractional crystallization of chromite and magnetite, whereas Ru anomalies are mainly due to variable degrees of compatibility of PGE in magnetite. The order of relative incompatibility of PGEs is calculated to be Pd?<?Pt?<?Rh?<?Ir?<?Ru. The very low PGE contents and Cu/Zr ratios and high Cu/Pd ratios suggest initially S-saturated magma parents that were highly depleted in PGE, which mainly formed due to low degrees of partial melting leaving sulfides concentrating PGEs behind in the mantle. Moreover, the low MgO, Ni, Ir and Ru contents and high Cu/Ni and Pd/Ir ratios for the gabbros suggest a highly evolved parental magma. Fe–Ti oxides fractionally crystallized from the highly evolved magma and subsequently settled in the lower sections of the magma chamber, where they concentrated and formed Fe–Ti–V oxide ore layers at the base of the lower and upper cycles. Multiple episodes of magma replenishment in the magma chamber may have been involved in the formation of the Zhuqing intrusions.     

PGE fractionation in seafloor hydrothermal systems: examples from mafic- and ultramafic-hosted hydrothermal fields at the slow-spreading Mid-Atlantic Ridge

The distribution of platinum group elements (PGEs) in massive sulfides and hematite–magnetite±pyrite assemblages from the recently discovered basalt-hosted Turtle Pits hydrothermal field and in massive sulfides from the ultramafic-hosted Logatchev vent field both on the Mid-Atlantic Ridge was studied and compared to that from selected ancient volcanic-hosted massive sulfide (VHMS) deposits. Cu-rich samples from black smoker chimneys of both vent fields are enriched in Pd and Rh (Pd up to 227 ppb and Rh up to 149 ppb) when compared to hematite–magnetite-rich samples from Turtle Pits (Pd up to 10 ppb, Rh up to 1.9 ppb). A significant positive correlation was established between Cu and Rh in sulfide samples from Turtle Pits. PGE chondrite-normalized patterns (with a positive Rh anomaly and Pd and Au enrichment), Pd/Pt and Pd/Au ratios close to global MORB, and high values of Pd/Ir and Pt/Ir ratios indicate mafic source rock and seawater involvement in the hydrothermal system at Turtle Pits. Similarly shaped PGE chondrite-normalized patterns and high values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides at Logatchev likely reflect a similar mechanism of PGE enrichment but with involvement of ultramafic source rocks.     

吉林省桦甸油页岩中稀土元素和微量元素的研究

对桦甸油页岩及其灰渣的矿物成分、主量元素、稀土元素和微量元素含量进行测定。结果表明：油页岩中稀土元素含量低于北美页岩(NASC)中的平均含量,REE球粒陨石标准化的分布模式曲线表现为负斜率,(La/Yb)_N的平均值大于1,属于轻稀土富集型;REE北美页岩标准化的分布模式曲线较平缓,（La/Yb）_S的平均值接近于1,轻重稀土分馏不明显。与球粒陨石和北美页岩相比,Eu有较严重的正异常。油页岩中的微量元素与北美页岩和地壳的平均值相比较,Sb、Nb、Cs、Zn、Bi、W等元素具有较高的富集度。油页岩灰渣中稀土元素和微量元素富集度均高于油页岩。     

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.