金川铜镍硫化物矿床中铂族矿物的主要类型和产出特征:热液蚀变过程中铂族元素的富集机理

金川铜镍硫化物矿床是我国最主要的铂族元素(PGE)资源产地,其矿石受热液蚀变作用影响明显,并产出多种铂族矿物(PGM)。岩浆演化和热液蚀变过程中PGE的迁移富集机制和PGM的成因,一直是研究PGE地球化学行为非常关注的问题。本文对金川铜镍硫化物矿床中PGM的研究发现,其主要类型包括含PGE的硫砷化物(硫砷铱矿)和砷化物(砷铂矿),Pd的铋化物、碲化物和硒化物,以及少量其他铂族矿物。其中,硫砷铱矿可包裹于各种贱金属硫化物(镍黄铁矿、磁黄铁矿和黄铜矿)中,表明硫砷铱矿可能结晶于早期的含As硫化物熔体,随后被包裹于硫化物熔体冷凝分异产生的单硫化物固溶体(MSS)和中间硫化物固溶体(ISS)中。硫化物熔体中的As可能主要通过地壳混染作用加入幔源岩浆。大量铋钯矿(PdBi)呈微细乳滴状包裹于黄铜矿中,为晚期ISS冷凝形成黄铜矿过程中出溶的产物。少量铋钯矿(PdBi_2)呈不规则状充填于矿物裂隙,与次生磁铁矿脉紧密共生,并随矿石的蚀变程度增加,铋钯矿的化学成分由PdBi逐渐向PdBi_2转变,表明这部分铋钯矿为后期热液蚀变产物。铋碲钯矿和钯的硒化物则主要产出于镍黄铁矿裂隙且与次生磁铁矿紧密共生,指示明显的热液成因。钯的硒化物的出现表明,岩浆期后酸性、高盐度、高氧逸度的富Cl~-流体对金川铜镍硫化物矿床中Pd的迁移和富集起到了关键控制作用。     

金川铜镍矿床龙首矿区半金属元素与铂族元素地球化学特征及成因意义

岩浆硫化物矿床中的铂族元素矿物主要是与半金属元素的化合物,但有关这些半金属元素在岩浆系统中的行为的研究却甚少。对金川龙首矿区不同类型矿石的Cu、Ni、铂族元素和半金属元素的分析研究发现,在熔离过程中这些半金属元素会与铂族元素一起进入硫化物熔浆中,在硫化物熔浆分离结晶过程中倾向于在残余熔体中富集,在单硫化物固溶体分离过程中部分半金属元素趋于进入镍黄铁矿中。由于半金属元素与铂族元素(PGE),特别是Pt和Pd,具有很强的亲和力,所以在半金属元素达到铂族矿物结晶所需要的饱和浓度前,其存在会阻碍PGE进入金属硫化物(BMS)中。此外,金川矿床S/Se值的变化不仅受同化混染作用及硫化物熔离强度的影响,还受后期热液蚀变作用的影响。     

青海化隆地区拉水峡铜镍矿床地质、地球化学特征及成因

拉水峡铜镍矿床位于化隆基性—超基性岩带中,岩体几乎全岩发生铜、镍硫化物矿化,且已遭受强烈蚀变,以角闪岩为主。岩浆期主要金属硫化物矿物组合为磁黄铁矿、黄铜矿、镍黄铁矿;热液蚀变期主要有紫硫镍矿、黄铁矿、黄铜矿、针镍矿等;氧化表生期主要为含镍高岭石、含镍绿泥石、孔雀石等。矿石轻稀土元素富集和负Eu异常明显,说明岩浆演化过程中发生了大量斜长石等的分离结晶作用。∑PGE含量平均为2460.46×10-9,（Pd＋Pt）/（Os＋Ir＋Ru）值为0.40~2.00,表明铂族元素与岩浆深部熔离作用密切相关;但Pt/Pd（0.01~2.62）、Pd/Ir（0.91~8.77）说明热液作用对铂族元素具有一定的富集作用。S同位素组成变化范围很小,δ34S平均值为2.24‰,硫化物中的S以地幔S为主。拉水峡矿床的形成经历了岩浆融离贯入、热液叠加改造及表生氧化作用3个阶段。     

青海化隆地区拉水峡铜镍矿床地质、 地球化学特征及成因

拉水峡铜镍矿床位于化隆基性—超基性岩带中,岩体几乎全岩发生铜、镍硫化物矿化,且已遭受强烈蚀变,以角闪岩为主。岩浆期主要金属硫化物矿物组合为磁黄铁矿、黄铜矿、镍黄铁矿;热液蚀变期主要有紫硫镍矿、黄铁矿、黄铜矿、针镍矿等;氧化表生期主要为含镍高岭石、含镍绿泥石、孔雀石等。矿石轻稀土元素富集和负Eu异常明显,说明岩浆演化过程中发生了大量斜长石等的分离结晶作用。∑PGE含量平均为2460.46×10-9,(Pd+Pt)/(Os+Ir+Ru)值为0.40~2.00,表明铂族元素与岩浆深部熔离作用密切相关;但Pt/Pd(0.01~2.62)、Pd/Ir(0.91~8.77)说明热液作用对铂族元素具有一定的富集作用。S同位素组成变化范围很小,δ34S平均值为2.24‰,硫化物中的S以地幔S为主。拉水峡矿床的形成经历了岩浆融离贯入、热液叠加改造及表生氧化作用3个阶段。     

金川镍铜铂硫化物矿床矿石成因——来自铂族元素地球化学的证据

对金川镍铜铂硫化物矿床Ⅰ、Ⅱ矿区主矿体典型钻孔中的不同类型矿石进行了系统观察和铂族元素分布特征研究。金川矿床中星点状矿石、网状矿石、块状矿石PGE 总量依次降低,由西至东24 号、1 号、2 号矿体的PGE 总量亦具渐次降低趋势。形成块状矿石的硫化物熔体PGE 分异作用较星点状和网状矿石更充分; 块状矿石铂族元素分布特征显示其受晚期硫化物熔体分离结晶和单硫化物固溶体( MSS) 分离作用控制。研究结果表明: 星点状矿石是岩浆分离结晶过程中较快速度冷凝和就地硫化物熔离的结果; 而网状矿石可能是硫化物熔体经深部熔离但未经充分的硫化物分离结晶作用贯入的产物; 块状矿石成因定量模拟结果排除了R 因子控制作用,不同矿体中块状矿石由不同程度的单硫化物固溶体( MSS) 分离结晶所形成。     

云南牟定安益铂钯钛磁铁矿床铂族矿物特征及成因初探

云南牟定安益矿床为一处铂族金属与钛磁铁矿共同产出的大型钛磁铁矿铂族金属矿床。目前对该矿床中铂族元素的赋存状态研究甚少。结合野外宏观地质特征和室内岩矿鉴定,笔者利用TIMA和LA-ICP-MS-Mapping分析方法,对安益矿床中铂族金属矿物学特征进行研究,发现安益矿床中的铂族元素（PGEs）主要以独立矿物的形式存在。铂族矿物（PGMs）多为铂和钯的砷化物、碲化物,如砷铂矿、砷钯矿、黄碲钯矿、碲钯矿等;主要分布于硅酸盐矿物中,其次为硫化物边缘,部分分布于磁铁矿边缘;铂族矿物成因主要有岩浆成因和热液成因2种。岩浆作用形成的铂族矿物分布于硅酸盐矿物中或硫化物边缘,硅酸盐中的铂族矿物是早期PGE与半金属元素形成的纳米团簇颗粒随岩浆演化形成矿物颗粒,被结晶的硅酸盐矿物包裹;分布于硫化物边缘的铂族矿物是残余熔浆结晶的结果。热液作用将PGE以类质同象的形式富集于钛磁铁矿单辉岩的部分矿物中,如热液蚀变较强烈的黄铜矿中含有较高的Rh,这也与铂族矿物集中分布在钛磁铁矿单辉岩中一致。     

布什维尔德铂族元素矿床:铂族矿物赋存状态及其成因

总结南非布什维尔德杂岩体中Merensky Reef(简称MR矿层)和Platreef(简称PR接触带)两类铂族元素矿床的矿床地质、矿化特征以及铂族元素的赋存状态。MR矿床是典型的层状铂族元素(PGE)矿床,在杂岩体东部和西部发育,PGE总含量稳定,赋存在堆晶间隙硫化物中,常以PGE硫化物的形式产出。PR接触带型矿化集中在杂岩体北段,整体上不连续,各个矿床的具体特征由于底盘岩性的多变而不同,PGE主要赋存在碲化物和砷化物等半金属化合物中,可以脱离硫化物产在硅酸盐矿物中。相关的实验研究显示,PGE在岩浆结晶过程中发生分异,Pd/Ir比值体现了硫化物的分异程度;Pd比Pt更容易被氧化以及在热液中迁移,Pt/Pd比值体现了混染和热液的作用,这些因素造成了PR接触带与MR矿层中PGE赋存状态的差异。岩浆可能在侵入之前已经达到了硫饱和,岩浆房的压力变化和岩浆通道对于PGE的富集有重要意义,热液流体可以对已经形成的PGE矿化进行改造。     

新疆北山红石山含铜镍镁铁-超镁铁质岩体PGE和Re-Os同位素地球化学特征及成矿意义

对新疆北山地区红石山镁铁-超镁铁质岩体中含铜镍的硫化物矿石和岩石进行了铂族元素和Re-Os同位素地球化学特征研究,结果表明,矿石及岩石的铂族元素(PGE)总量较低,变化于0.54×10-9~15.84×10-9之间。较低的Pd/Ir比值表明岩石主要受岩浆作用控制,后期热液作用影响不明显。较高的Cu/Pd和Ti/Pd比值表明岩浆在演化过程中发生了硫化物的熔离。岩体的母岩浆为有早期结晶橄榄石加入的高镁的玄武质岩浆。γOs(t)的变化较大,变化于-282~+282之间,表明有较多的地壳物质混入。地壳物质混染和橄榄石等矿物的分离结晶可能是引起岩浆中的S达到饱和进而熔离的重要因素。红石山岩体是经历了结晶分异和硫化物熔离后橄榄石的堆积体与残余岩浆演化的混合体。     

四川攀枝花新元古代苦橄质岩脉的铂族元素地球化学特征

四川攀枝花地区出露有新元古代苦橄质岩脉。本文研究表明这些苦橄质岩脉的铂族元素(PGE)含量较高(19.7~29.0 ng/g),原始地幔标准化后的PGE分布模式呈Pt-Pd富集型,Pd/Ir值(5.64~11.33)与高镁玄武岩和科马提岩相似。同时,这些岩石显示在形成过程中没有经历硫化物和PGE合金矿物的熔离,其原始岩浆起源于地幔较高程度的部分熔融,可能与地幔柱的影响有关。通过扣除铬尖晶石和橄榄石结晶分异对PGE造成的影响,得到原始岩浆的PGE组成特征为Ir、Ru、Rh相对于Pt、Pd明显亏损,在源区已无硫化物存在的条件下,这很可能是由于地幔部分熔融过程中有IPGE合金矿物残留在地幔源区。攀枝花地区苦橄质岩脉可能与该地区冷水箐Cu-Ni硫化物矿床具有相似的原始岩浆组成。     

新疆哈密白石泉含铜镍镁铁-超镁铁质岩体铂族元素特征

新疆哈密白石泉镁铁-超镁铁质岩体的铂族元素研究表明,岩体的铂族元素总含量较低,原始地幔标准化模式具镁铁质岩石的特征,并具Pt 正异常,且铂族元素的分异主要受结晶分异作用的影响.岩体的Cu/Pd、Se/S、Ti/Pd值表明其发生过硫化物的熔离作用.Pd/Ir、Ni/Cu特征表明了岩体系高镁玄武岩岩浆的产物.铂族元素特征揭示了白石泉岩体硫化物的熔离作用是由原始岩浆结晶分异导致的,岩体的形成是原始岩浆发生橄榄石等的结晶,导致硫化物的熔离作用后,其残余岩浆演化的结果.     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

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.     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

Bellechester,Minnesota, USA,lagoon collapses

Bellechester, Minnesota, is a small community of approximately 155 residents located on the county line between Goodhue and Wabasha counties in southeast Minnesota's karst region. Bellechester is served by a 21-year-old wastewater treatment facility (WWTF) consisting of three waste-stabilization ponds. On 28 April 1992 six sinkholes were discovered to have drained cell 2 of the WWTF resulting in the loss of approximately 8.7×10⁶ 1 of partially treated effluent and about 600 m³ of soil into previously undetected subsurface voids of unknown dimensions. In the week following the collapse, approximately 200 water wells located within a 5-km radius of the WWTF were sampled in an after-the-fact, emergency sampling program. Twelve samples with elevated fecal coliform levels, 18 samples with nitrate-nitrogen greater than the 10 mg/1 standard, and no samples with elevated chlorides were found. However, the elevated levels could not be unambiguously attributed to the WWTF collapse. This is the third WWTF to fail by sinkhole collapse in southeast Minnesota since 1974. All three collapsed lagoons have been located in similar geomorphic and stratigraphic settings. However, at least two lagoons have collapsed in the adjacent area in northeast Iowa, and these lagoons are located at different stratigraphic positions. Twenty-two WWTFs constructed in southeast Minnesota's karst region in the last 25 years have been identified as subject to potential sinkhole collapse. An unknown but significant number of manure storage lagoons, flood control structures, etc., have also been constructed in the karst region and are at risk. Public agencies are beginning to develop plans to deal with the risk associated with existing and future waste lagoons in this environment. The critical hydrogeologic parameters that can be used to prioritize the risk of collapse at existing facilities include: (1) the lithology of the first bedrock beneath each lagoon, (2) the thickness of surficial materials between the lagoon and the bedrock surface, (3) the presence and construction of liners (seepage rate), and (4) the proximity to existing sinkholes.     

Mercury,arsenic, antimony,and selenium contents of sediment from the Kuskokwim River,Bethel, Alaska,USA

The Kuskokwim River at Bethel, Alaska, drains a major mercury-antimony metallogenic province in its upper reaches and tributaries. Bethel (population 4000) is situated on the Kuskokwim floodplain and also draws its water supply from wells located in river-deposited sediment. A boring through overbank and floodplain sediment has provided material to establish a baseline datum for sediment-hosted heavy metals. Mercury (total), arsenic, antimony, and selenium contents were determined; aluminum was also determined and used as normalizing factor. The contents of the heavy metals were relatively constant with depth and do not reflect any potential enrichment from upstream contaminant sources.     

滇东南花岗岩与锡、银、铜、铅、锌多金属矿床的成因关系

滇东南锡、银、铅、锌多金属矿床主要分布在个旧、白牛厂、都龙3个矿区,而滇东南较大的3个花岗岩体又分别出露在3个矿区或附近.花岗岩体均形成于燕山晚期,岩石化学、矿物成分相似,富含锡、银、铅、锌、钨、铜等成矿元素.矿床主金属元素组合与岩体之间的距离由远而近出现由锡、钨、(铍、铌、钽)→锡、钨、(铁)、铜、铟→锡、铅、锌、银、铟、(锑)有规律的变化.花岗岩浆是成矿物质来源和成矿热源.岩浆侵入初期使上覆地层隆起产生背斜(凹陷部位成向斜);同时使地层产生一系列裂隙、压性断层或层间断裂;岩浆侵入晚期,这些断层再次活动,表现为张性,岩浆产生的含矿热液沿由其活动所造成的断裂迁移、充填、交代、沉淀而形成矿床.     

岩石密度和超高压岩石折返速率

在常温常压条件下对中国大陆科学钻CCSD主孔100-3000米岩心样品进行了密度测量,建立了密度连续剖面,并界定了不同超高压岩石的密度值。通过对比高温高压物性实验资料,岩石密度随着退变程度增强而降低,榴辉岩密度变化序列为3.52g/cm3→3.49g/cm3→3.07g/cm3→2.93g/cm3。超高压长英质岩石密度变化序列为3.00g/cm→2.80g/cm3→2.65g/cm3。上述实验资料是讨论不同折返阶段岩石所受浮力的基础,为研究折返速率大小提供了基本参数。本文通过折返板块运动平衡时,上浮力与粘滞力平衡这一关系式,定量研究了大陆俯冲板块的折返速率,认为密度差产生上浮力从而引起折返,温度对板块折返速率的影响最为显著;密度差大小、折返角度、折返板块大小对折返速率也有直接的影响。定量模拟分析表明,在温度高于850℃时,板块的折返速率可以超过100mm/a;当温度降至700℃时,折返速率则低于1.5mm/a。作者认为在折返早期,温度较高,板块快速折返至60-70km榴辉岩相深度;随着传导散热,温度降低,板块以较慢的速率折返至中下地壳。折返速率的估算表明,浮力是板块折返第一阶段(从>100km深部折返至<40km的中下地壳)的主要驱动力。