亲铜(亲铁)元素含量比值在地球科学中的初步应用实例

亲铜(亲铁)元素在行星增生演化、核幔分异、地幔岩浆过程、壳幔相互作用以及金属矿床成因等领域具有举足轻重的作用。本文从亲铜元素的地球化学性质出发,介绍了"高维度思维"的亲铜元素含量比值及其在地球科学领域的初步应用:①获得同一份样品中不同亲铜元素含量可在一定程度上降低样品的不均一性(块金效应)对含量比值的影响;②Cu/Ag值可以约束不同高温岩浆过程中硫化物固液状态和亲铜元素地球化学性质,进而认识地幔、洋壳和大陆地壳间的联系;③具有不同分配系数的亲铜元素含量的比值可以鉴别岩浆硫化物饱和史,比如通过亲铜元素的分异约束火星陨石母岩浆的硫化物不饱和演化历史;④依据In-Cd-Zn在硅酸盐地球的含量以及它们的相对亲铜亲铁性质,地球主体增生物质已经消失,不能由陨石代表。     

Behavior of Siderophile and Chalcophile Elements in the Subcontinental Lithospheric Mantle beneath the Changbaishan Volcano,NE China

The mantle xenoliths in the Quaternary ChangbaishanVolcano in southern Jilin Province contain spinel-facies lherzolites. The equilibration temperatures for these samples range from 902oC to 1064oC based on the two-pyroxene thermometer of Brey and K?hler (1990), and using the oxybarometry of Nell and Wood (1991), the oxidation state was estimated from FMQ-1.32 to -0.38 with an average value of FMQ-0.81 (n?=?8), which is comparable to that of abyssal peridotites and the asthenospheric mantle. The fO2 values of peridotites, together with their bulk rock compositions (e.g., Mg#, Al2O3, CaO, Ni, Co, Cr) and mineral compositions (e.g., Mg# of olivine and pyroxene, Cr# [=Cr/[Cr+Al]] and Mg# [=Mg/[Mg+Fe2+] of spinel), suggest that the present-day subcontinental lithospheric mantle (SCLM) beneath the Changbaishan Volcano most likely formed from an upwelling asthenosphere at some time after the late Mesozoic and has undergone a low degree of partial melting. The studied lherzolite xenoliths show low concentrations of S, Cu, and platinum group elements (PGE), which plot a flat pattern on primitive-mantle normalized diagram. Very low concentrations in our samples suggest that PGEs occur as alloys or hosted by silicate and oxide minerals. The compositions of the studied samples are similar to those of peridotite xenoliths in the Longgang volcanic field (LVF) in their mineralogy and bulk rock compositions including the abundance of chalcophile and siderophile elements. However, they are distinctly different from those of peridotite xenoliths in other areas of the North China Craton (NCC) in terms of Cu, S and PGE. Our data suggest that the SCLM underlying the northeastern part of the NCC may represent a distinct unit of the newly formed lithospheric mantle.     

强亲铁元素高温地球化学与天体化学及研究进展

强亲铁元素(HSE)包括铂族元素(PGE):Os、Ir、Ru、Rh、Pt、Pd)及Re、Au,它们对金属与硫化物相具有强烈的亲和性,这种独特性质使其成为高温地球化学与天体化学研究中的优秀示踪剂。此外,强亲铁元素内含两种长半衰期(¹⁸⁷Re-¹⁸⁷Os,t_1/2=41.6 Ga;¹⁹⁰Pt-¹⁸⁶Os,t_1/2=469 Ga)和一种短半衰期(¹⁰⁷Pd-¹⁰⁷Ag,t_1/2=6.5 Ma)放射性同位素衰变体系,可以用作地球与天体演化的时钟。在地幔部分熔融或分离结晶期间,PPGE(Rh、Pd、Pt)与Re、Au倾向于进入熔体相,IPGE(Os、Ir、Ru)则更多保留在残余固相。因此,通过地幔包体、地幔构造岩、镁铁质与超镁铁质火山岩的HSE丰度与Os同位素可约束地幔组成和相应的岩浆过程,以及制约地球早期演化过程。随着分析技术的改进,HSE与Re-Pt-Os同位素在行星增生与分异、核幔相互作用、壳幔分异、洋陆转换、克拉通形成与破坏、岩石圈俯冲再循环以及Ni-Cu-PGE矿床成因等方面均显示了巨大的应用潜力。     

A Method to Suppress Isobaric and Polyatomic Interferences for Measurements of Highly Siderophile Elements in Desilicified Geological Samples

Sample decomposition using inverse aqua regia at elevated temperatures and pressures (e.g., Carius tube or high‐pressure asher) is the most common method used to extract highly siderophile elements (HSEs: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) from geological samples. Recently, it has been recognised that additional HF desilicification is necessary to better recover HSEs, potentially contained within silicate or oxide minerals in mafic samples, which cannot be dissolved solely by inverse aqua regia. However, the abundance of interfering elements tends to increase in the eluent when conventional ion‐exchange purification procedures are applied to desilicified samples. In this study, we developed an improved purification method to determine HSEs in desilicified samples. This method enables the reduction of the ratios of isobaric and polyatomic interferences, relative to the measured intensities of HSE isotope masses, to less than a few hundred parts per million. Furthermore, the total procedural blanks are either comparable to or lower than conventional methods. Thus, this method allows accurate and precise HSE measurements in mafic and ultramafic geological samples, without the need for interference corrections. Moreover, the problem of increased interfering elements, such as Zr for Pd and Cr for Ru, is circumvented for the desilicified samples.     

苏鲁超高压变质带中蛇纹岩的地球化学特征及岩石成因

青岛的仰口和日照的梭罗树是苏鲁超高压变质带中重要的蛇纹岩出露区。系统的岩石地球化学分析表明,仰口和梭罗树地区的蛇纹岩具有高Mg、低Al_2O_3/Si O_2、贫高场强元素(Nb、Th、Zr和Hf)和重稀土元素(HREE)的特征,其原岩是经历了不同程度部分熔融后的地幔残余,符合弧前地幔橄榄岩的特征。经模拟估算,仰口蛇纹岩的原岩熔融程度15%,梭罗树蛇纹岩的原岩熔融程度在20%~25%之间。蛇纹岩富流体迁移元素(U、Pb和LREE),且LREE和HFSE无明显相关性的地球化学特征表明,研究区蛇纹岩原岩在弧前地幔楔环境下,受到俯冲板片释放的含H_2O流体作用发生蛇纹石化,形成了流体迁移元素富集的蛇纹岩。     

Osmium isotope and highly siderophile element geochemistry of mantle xenoliths from NW Turkey: implications for melt depletion and metasomatic history of the sub-continental lithospheric mantle

Ultramafic xenoliths entrained in the late Miocene alkali basalts and basanites from NW Turkey include refractory spinel-harzburgites and dunites accompanied by subordinate spinel-lherzolites. Whole-rock major and trace element characteristics indicate that the xenoliths are mostly the solid residues of varying degrees of partial melting (～4–～15%), but some have geochemical signatures reflecting the processes of melt/rock interaction. Mantle-normalized trace element patterns for the peridotites vary from LREE-depleted to strongly LREE-enriched, reflecting multistage mantle processes from simple melt extraction to metasomatic enrichment. Rhenium and platinum group element (PGE) abundances and ¹⁸⁷Os/¹⁸⁸Os systematics of peridotites were examined in order to identify the nature of the mantle source and the processes effective during variable stages of melt extraction within the sub-continental lithospheric mantle (SCLM). The peridotites are characterized by chondritic Os/Ir and Pt/Ir ratios and slightly supra-chondritic Pd/Ir and Rh/Ir ratios, representing a mantle region similar in composition to the primitive mantle (PM). Moderate enrichment in PPGE (Pd–Pt–Rh)/IPGE (Ir–Os–Ru) ratios with respect to the PM composition in the metasomatized samples, however, reflects compositional modification by sulphide addition during possible post-melting processes. The ¹⁸⁷Os/¹⁸⁸Os ratios of the peridotites range from 0.11801 to 0.12657. Highly unradiogenic Os isotope compositions (γOs at 10 Ma from –7.0 to –3.2) in the chemically undisturbed mantle residues are accompanied by depletion in Re/Os ratios, suggesting long-term differentiation of SCLM by continuous melt extraction. For the metasomatized peridotites, however, systematic enrichments in PPGE and Re abundances, and the observed positive covariance between ¹⁸⁷Re/¹⁸⁸Os and γOs can most likely be explained by interaction of solid residues with basaltic melts produced by melting of relatively more radiogenic components in the mantle. Significantly, the wide range of ¹⁸⁷Os/¹⁸⁸Os ratios characterizing the entire xenolith suite seems to be consistent with multistage evolution of SCLM and suggests that parts of the lithospheric mantle contain materials that have experienced ancient melt removal (～1.3 Ga) which created time-integrated depletion in Re/Os ratios; in contrast, some other parts display evidence indicative of recent perturbation in the Re–Os system by sulphide addition during interaction with metasomatizing melts.     

软流圈熔体地幔交代作用过程中的铂族元素行为

南美洲南部的Pali Aike火山岩区第四纪碱性玄武岩中普遍发育含石榴石的斜方辉石岩包体。这种斜方辉石岩既作为独立的捕掳体存在又以细脉的形式穿插于橄榄岩捕掳体中。斜方辉石岩普遍含富Ti矿物,并且次生斜方辉石含橄榄石和单斜辉石残晶。与含石榴石橄榄岩中的斜方辉石相比,这种次生的斜方辉石以高TiO2、中等含量的Al2O3以及低Mg#为特征,表明它是在一种高度分异演化的富Ti熔体交代作用下通过消耗橄榄石和单斜辉石方式形成的。斜方辉石岩全岩的Co、Ni略低,Cr和铂族元素(PGE)含量与地幔橄榄岩相当,表明这些元素在交代作用过程中相对稳定,而交代介质带入的组分以碱质(K2O+Na2O)、Ti、Si、Al和S为主。交代的斜方辉石在现代活动岛弧和古克拉通的地幔橄榄岩捕掳体中多有报道。与这些环境中地幔样品的斜方辉石相比,PaliAike地区的次生斜方辉石含有相对高的Ti和Al,以及相对低的Mg。高Ti低Mg属性反映了交代介质可能来源于下伏的软流圈地幔并且经历了高度的分异和演化过程。Pali Aike地区所见到的这种交代斜方辉石和斜方辉石岩在其他被上涌软流圈影响的陆下岩石圈地幔中可能普遍存在。这些研究对了解中国华北-东北中生代以来的岩石圈地幔减薄机制有着重要的借鉴意义。     

Siderophile elements in chondrules of CV chondrites

New bulk compositional data for 34 Allende chondrules are presented. Whole chondrules were analyzed by instrumental neutron activation analysis (INAA). The new data set is evaluated together with older INAA data on Allende chondrules and recent INAA data on Mokoia chondrules. The Ni/Co ratios of 200 chondrules are close to the CI- or solar ratio. The chondritic Ni/Co ratios require an unfractionated chondritic metal source and set a limit to the fraction of metal lost from molten chondrules. The bulk chondrule Fe/Ni and Fe/Co ratios are more variable but on average chondritic. Iridium and other refractory metals have extremely variable concentrations in chondrules. High Ir chondrules have chondritic Ir/Sc ratios. They are dominated by CAI (Ca,Al-rich inclusion) components. Low Ir chondrules have approximately chondritic Ir/Ni ratios reflecting mixing with chondritic metal. In low Ir chondrules Ir correlates and in high Ir chondrules Ir does not correlate with Ni or Co. A large fraction of Ir may have entered chondrules in variable amounts as tiny grains of refractory metal alloys.Most Allende chondrules have Ir/Sc ratios below bulk meteorite ratios. Matrix must have a complementary high Ir/Sc ratio, as bulk Allende has approximately chondritic Ir/Sc ratio. Similarly, the high average Ir/Ni ratios of Allende chondrules must be balanced by low Ir/Ni ratios in matrix to obtain the bulk Allende Ir/Ni ratio, which is close to the average solar system ratio.More recent data on single chondrules from Allende by ICP-MS (Inductively Coupled Plasma Mass Spectrometry) and ICP-OES (Inductively Coupled Optical Emission Spectrometry) show the same trends as the INAA data discussed here.     

西藏西南部达巴-休古嘎布蛇绿岩带中地幔橄榄岩的成因

本文报道了西藏西南部达巴-休古嘎布蛇绿岩带中橄榄岩的矿物化学资料.橄榄岩中主要造岩矿物化学成分的分析研究表明,该区橄榄岩为残余地幔成因,但它们不是地幔简单熔化的残余物.尖晶石中Cr#及辉石中Ti的广泛变化表明它们具有复杂的熔融历史及地幔交代作用的印记,其形成过程可能经历了两种构造环境的转变.早期在MORB环境下形成低Cr#(尖晶石)橄榄岩;其后由于洋内俯冲作用,早先形成的低熔橄榄岩被消减到岛弧之下再度发生熔融形成高Cr#(尖晶石)橄榄岩.从而,在古大洋消失之后形成的碰撞带上同时保存了MORB型和SSZ型两类蛇绿岩.     

Chemical Analysis of Iron Meteorites by Inductively Coupled Plasma-Mass Spectrometry

Iron meteorites were analysed for nineteen siderophile and chalcophile elements by conventional inductively coupled plasma-mass spectrometry with the specific aim of demonstrating that this technique is an effective alternative to the more routine, yet complex, methodologies adopted in this field such as instrumental or radiochemical neutron activation analysis. Two aliquots of each meteorite sample, in the form of small shavings, were dissolved, one in 6 mol l^-1 HNO₃ and the other in aqua regia , and diluted to a final concentration of 1 mg sample per 1 ml of solution, without pre-concentrating the analytes. Nitric acid solutions were used for the determination of the elements Cr, Co, Ni, Cu, Ga, Ge and As; aqua regia solutions were analysed for the elements Mo, Ru, Rh, Pd, In, Sn, Sb, W, Re, Ir, Pt and Au. Samples were analysed by external calibration, carried out using synthetic multi-elemental solutions, and internal standardisation (with Be, Rb and Bi selected as internal standards). The results obtained from the analyses of nine geochemically well-characterized iron meteorites (Canyon Diablo, Odessa, Toluca, Coahuila, Sikhote-Alin, Buenaventura, Tambo Quemado, Gibeon, NWA 859) with widely variable chemical compositions are in good agreement with literature values for most elements. Detection limits were generally below the lowest concentration observed in iron meteorites. The most notable exception is for Ge, which cannot be successfully determined in the low-Ge meteorites of groups IVA, IVB and IIIF and a number of ungrouped irons. A test of the overall reproducibility of the adopted method, undertaken by repeatedly analysing the same Odessa IAB meteorite specimen, yielded relative standard deviations (1 s ) of between 1 and 6% for all elements except Cr (40%).