Trace element abundance patterns of garnet inclusions in peridotite-suite diamonds

Individual, sub-calcic, chrome-pyrope crystals from Finsch and Kimberley diamonds, Finsch and Bultfontein kimberlite heavy mineral concentrate, and from diamondiferous harzburgite-dunite xenoliths from the Udachnaya kimberlite pipe were analyzed for rare earth elements (REE), Sc, Ti, and Zr with the ion microprobe. The abundances and abundance ratios of these trace elements including LREE enrichment and low Ti, together with high and variable Cr contents, are inconsistent with a simple equilibrium relationship between peridotite-suite garnet and silicate and carbonate liquids. It is suggested that the trace element abundance patterns represent a signature of ancient mantle metasomatism which preceded the formation of peridotite-suite garnet and diamond.     

Enrichment processes at the base of the Archean lithospheric mantle: observations from trace element characteristics of pyropic garnet inclusions in diamonds

Trace element concentrations of peridotitic garnet inclusions in diamonds from two Chinese kimberlite pipes were determined using the ion microprobe. Garnet xenocrysts from the same two kimberlite pipes were also analyzed for comparison. In contrast to their extremely refractory major element compositions, all harzburgitic garnets showed enrichment in light rare earth elements (REE) relative to chondrite, resulting in sinuous REE patterns. Both normal and sinuous REE patterns were observed from the lherzolitic garnets. Concentrations of REE in garnets changed significantly from diamond to diamond and no specific correlations were observed with their major element compositions. Analyses of randomly selected two to three points within every grain of a large number of garnet inclusions by the ion microprobe demonstrated that there was no evident compositional heterogeneity, and multiple grains of one phase from a single diamond host also exhibit very similar compositions. This implies that the trace element heterogeneity within one grain or among multiple inclusions from the same diamond host, as reported from Siberian diamonds, is not a common feature for these Chinese diamonds. Concentrations of Na, Ti, and Zr tend to decrease when garnets become more refractory, but variations of Sr and Li are more complex. Compositions rich in light REE and relatively poor in high field strength elements (HFSE) of the harzburgitic garnet inclusions in diamonds are generally consistent with metasomatism by carbonatite melts. The trace element features observed from the garnet inclusions in Chinese diamonds may be caused by carbonatite melt infiltration and partial melt extraction. Spatial and temporal gradients in melt/rock ratio and temperature are the main reasons for the large variations of REE patterns and other trace element concentrations. Received: 27 April 1999 / Accepted: 1 March 2000     

Methodology for Rare Earth Element Determinations of Uranium Oxides by Ion Microprobe

A methodology for the determination of the rare earth elements in uranium oxides by ion microprobe has been set up on a Cameca ims-3f instrument. An uranium oxide reference material from a syn-metamorphic uranium deposit related to albitisation has also been developed for this type of analysis. Applications of the methodology are presented for a series of uranium oxides selected from some major uranium deposit types: from the world's highest grade unconformity-related uranium deposit from the Athabasca Basin (Saskatchewan, Canada; the Shea Creek and the McArthur River examples), a perigranitic vein-type deposit (Pen Ar Ran, Vendée, France) and a volcanic caldera-related deposit (Streltsovkoye, Transbaikalia, Russia). Each type of uranium deposit appears to have a specific REE signature. All REE patterns from the Shea Creek and the McArthur deposits are characterised by bell-shaped patterns centred on Tb-Dy and similar to those already published for uranium oxides from unconformity-related deposits from Australia. Such bell-shaped REE patterns centred on Tb-Dy may therefore be considered as a typical signature of uranium oxides from Mesoproterozoic unconformity-related deposits. A smoother bell shape pattern centred on Eu characterises the syn-metamorphic albitisation related deposit of Mistamisk selected for the reference material. The REE patterns from the Pen Ar Ran deposit show a fractionation from LREE to HREE with anomalously high abundances of Sm, Eu and Gd with respect to the other REEs, similar to the REE patterns of uranium oxides from the volcanic-related deposits of Streltsovkoye.     

Polycrystalline amphibole aggregates (clots) in granites as potential I‐type restite: An ion microprobe study of rare‐earth distributions

Aggregates of polycrystalline grains of amphibole (clots) occur widely in the granodiorites of the Strontian pluton, Scotland. These clots are complex structures with numerous small grains in the interior exhibiting zonation from actinolite cores to hornblende rims. Amphiboles in the outer parts of these clots are indistinguishable from hornblendes that have crystallised from the melt. A rare‐earth element (REE) study of individual amphibole and pyroxene grains using an ion microprobe has also shown a marked difference in REE abundances, with clots generally being depleted in their interiors. Modelling of the compositions shows that the clots are consistent with being derived from pyroxene + plagioclase ± amphibole precursors. These granular precursors are recognised as being consistent with the residual crystalline material encountered in dehydration melting experiments of amphibolitic starting materials. It is suggested that these features could represent restite in I‐type granodiorites and tonalites. Extensive, but incomplete equilibration of the clot material provides an explanation for the infrequent identification of restite (other than grain cores) in I‐type granites, in marked contrast with S‐types.     

RARE EARTH ELEMENT CONCENTRATIONS IN USGS AND CCRMP IGNEOUS ROCK STANDARDS DETERMINED BY HIGH PERFORMANCE ION CHROMATOGRAPHY

Eleven rare earth elements (REE) have been determined in ten USGS and two CCRMP igneous rock standards using high performance ion chromatography. Duplicate analyses of two or more separately prepared aliquots of each sample were undertaken; reproducibility was better than 5% for each of the REE. In most cases, the results compare closely with published REE values for those samples for which the REE are well characterised. Where the results for individual elements are in disagreement with published data, the more erratic patterns yielded by the earlier data when plotted on chondrite-normalised REE diagrams suggest that values determined in this study are of greater accuracy.     

广东禾尚田矿区新类型风化壳离子吸附型稀土矿的发现及意义

在广东禾尚田矿区,通过地表和钻孔岩芯样品的野外硫酸铵浸泡-草酸点滴试验、化学分析、稀土（REE）配分分析、稀土浸取率测定等工作,首次发现了灰岩风化壳中存在离子吸附型富铕稀土工业矿床。稀土矿与坡残积钨锡矿、铷矿共伴生,并伴生锂、镓和铯等元素,具有中稀土富集和高浸取率的特点,是离子吸附型稀土矿的新类型。它的发现将对离子吸附型稀土矿床勘查产生深远的影响,大大拓展找矿思路和对象;并说明了在一个矿田或一个矿区内寻找新的矿种、新的矿床类型、新的含矿层位的重要性。通过成矿地质条件分析,作者认为矿区西部找矿前景甚佳,禾尚田矿区将成为一个集有色、稀有、稀土、贵金属矿产的多矿种、多矿床类型、多含矿层位的矿区。     

Rare earth element geochemistry and petrogenesis of miles (IIE) silicate inclusions

An ion probe study of rare earth element (REE) geochemistry of silicate inclusions in the Miles IIE iron meteorite was carried out. Individual mineral phases among inclusions have distinct REE patterns and abundances. Most silicate grains have homogeneous REE abundances but show considerable intergrain variations between inclusions. A few pyroxene grains display normal igneous REE zoning. Phosphates (whitlockite and apatite) are highly enriched in REEs (50 to 2000 × CI) with a relatively light rare earth element (LREE)-enriched REE pattern. They usually occurred near the interfaces between inclusions and Fe host. In Miles, albitic glasses exhibit two distinctive REE patterns: a highly fractionated LREE-enriched (CI normalized La/Sm ∼15) pattern with a large positive Eu anomaly and a relatively heavy rare earth element (HREE)-enriched pattern (CI-normalized Lu/Gd ∼4) with a positive Eu anomaly and a negative Yb anomaly. The glass is generally depleted in REEs relative to CI chondrites.The bulk REE abundances for each inclusion, calculated from modal abundances, vary widely, from relatively depleted in REEs (0.1 to 3 × CI) with a fractionated HREE-enriched pattern to highly enriched in REEs (10 to 100 × CI) with a relatively LREE-enriched pattern. The estimated whole rock REE abundances for Miles are at ∼ 10 × CI with a relatively LREE-enriched pattern. This implies that Miles silicates could represent the product of a low degree (∼10%) partial melting of a chondritic source. Phenocrysts of pyroxene in pyroxene-glassy inclusions were not in equilibrium with coexisting albitic glass and they could have crystallized from a parental melt with REEs of ∼ 10 × CI. Albitic glass appears to have formed by remelting of preexisting feldspar + pyroxene + tridymite assemblage. Yb anomaly played an important role in differentiation processes of Miles silicate inclusions; however, its origin remains unsolved.The REE data from this study suggest that Miles, like Colomera and Weekeroo Station, formed when a molten Fe ball collided on a differentiated silicate regolith near the surface of an asteroid. Silicate fragments were mixed with molten Fe by the impact. Heat from molten Fe caused localized melting of feldspar + pyroxene + tridymite assemblage. The inclusions remained isolated from one another during subsequent rapid cooling.     

Ion Probe Study of Silicate Inclusions from Colomera （IIE） Iron Meteorite： the Rare Earth Element Perspective

Coupled with a petrographical study, I carried out an ion probe study of rare earth element microdistributions in mineral phases of silicate inclusions from the Colomera IIE iron meteorite. Most mineral grains have homogeneous REEs, but show considerable inter-grain variations by a factor of 2 to 100. The whole rock REE abundances for Colomera,estimated by combining REE data with modal abundances, are relatively LREE-enriched with REEs of～10’CI, which suggest that Colomera silicates were highly differentiated and might represent a low degree partial melt (-10%) of a chondritic source. REE geochemistry of Colomera silicate inclusions points to an origin that involves differentiation,dynamic mixing, remelting, reduction, recrystallization, and subsequent rapid cooling near the surface of a planetary body.     

Rare earth element patterns and crustal evolution—I. Australian post-Archean sedimentary rocks

A suite of Australian shales, greywackes and subgreywackes ranging in age from Proterozoic to Triassic were analyzed for the rare earth elements (REE) in order to detect any secular changes in rare earth distribution. These post-Archean sediments show remarkably similar relative rare earth patterns. They are characterized by negative Eu anomalies of almost constant magnitude (average Eu/Eu* = 0.67 ± 0.05) relative to chondrites and nearly constant ratios of light to heavy rare earths (average ∑LREE/∑HREE = 9.7 ± 1.8).

The REE abundances are generally higher in the younger sediments which may suggest that the absolute abundances of the rare earths in clastic sediments have gradually increased with time. Since no secular change in relative rare earth distribution was detected in the post-Archean sediments, a uniform process of crustal growth and evolution seems to have operated over the past 1500 million years at least.

Australites show rare earth distributions very similar to that of the average clastic sediment. This suggests that the tektite parent material originated in the upper crust.     

Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

Trace element geochemistry of the Mt Vulture carbonatites,southern Italy

The Mt Vulture carbonatites are the only carbonatite occurrence in the southern Apennines. We present new trace element data for these rocks in order to evaluate the factors influencing rare earth element (REE) and other trace element fractionations and their REE grade. This study focuses on massive hyalo-alvikites from two lava flows and one dike, which have different relative abundances of silicate and carbonate (i.e. Si/Ca). These differences are also evident from CaO/(CaO + MgO + FeO(T) + MnO) and Sr/Ba ratios. The REE grade of the Mt Vulture carbonatites is very similar to that of the global average for calcio-carbonatites. R-mode factor analysis shows that most of the trace element variance reflects the relative roles of carbonate and silicate minerals in influencing trace element distributions. Silicates largely control heavy rare earth element (HREE), transition metal, Zr, and Th abundances, whereas carbonate minerals control light rare earth element (LREE), Ba, and Pb abundances. In addition, apatite influences LREE concentrations. Increasing silica contents are accompanied by decreases in (La/Yb)N and (La/Sm)N ratios and less marked LREE enrichment. In contrast, higher carbonate contents are associated with increases in (La/Yb)N and (La/Sm)N. The Si/Ca ratio has little influence on Eu anomalies and middle rare earth element (MREE) to HREE fractionations. Apatite has a negligible effect on inter-REE fractionations amongst the carbonatites.     

Trace element concentrations in silicate spherules from oceanic sediments

The possible existence of meteoritic spherules was investigated among several silicate spherules separated from oceanic sediments and analyzed by means of INAA (instrumental neutron activation analysis).A 0.72 mg glassy spherule was found to have uniform enrichment of 4 ~ 5 for the refractory REE (rare earth elements) and Sc with substantial depletion of Ce relative to chondritic abundances. This implies that this spherule is meteoritic in origin and that the enrichment of refractory elements was established by high temperature heating in a high O/H environment, possibly at the time of entering the Earth's atmosphere.The other three analyzed spherules showed major and trace element abundances that are consistent with an origin in the oceanic environment.     

Rare earth element partitioning between minerals from anhydrous spinel peridotite xenoliths

REE abundances in minerals from spinel peridotite xenoliths from West Germany, the south-western U.S. and Mongolia decrease in the order clinopyroxene > orthopyroxene > olivine > spinel. While clinopyroxenes are similar in absolute chondrite-normalized concentrations to those known from other studies, orthopyroxenes and olivines are significantly lower in LREE although comparable in HREE. Spinels are much lower in all REE than any previously reported values and are completely negligible for the REE budget of peridotites.Partition coefficients for most orthopyroxene/clinopyroxene pairs increase systematically from La to Lu. Olivine/clinopyroxene and spinel/clinopyroxene partition coefficients increase from the intermediate rare earth elements to Lu and normally are higher for La compared to Sm.The application of Nagasawa's (1966) elastic lattice model suggests that all heavy but only minor amounts of the light REE substitute into structural positions of orthopyroxene and olivine.Significant differences between orthopyroxene/clinopyroxene partition coefficients for various xenoliths may be assigned to dependences upon equilibration temperature and bulk chemistry.Apart from grain surface contaminations, fluid inclusions which are practically always present in mantle minerals, can highly concentrate light rare earth elements and thus may be responsible for unexpectedly high concentrations of incompatible elements frequently reported for mantle olivines or orthopyroxenes.     

Elemental composition of individual chondrules from carbonaceous chondrites,including Allende

Major and trace element analyses of over 180 individual chondrules from 12 carbonaceous chondrites are reported, including individual analyses of 60 chondrules from Pueblito de Allende. Siderophile elements in most chondrules are depleted, compared to the whole chondrite. Correlations of Al-Ir and Ir-Sc among chondrules high in Ca and Al were observed. A Cu-Mn correlation was also found for chondrules from some meteorites. No correlation was observed between Au and other siderophile elements (Fe, Ni, Co and Ir). It is suggested that these elemental associations were present in the material from which the chondrules formed. Compositionally, chondrules appear to be a multicomponent mixture of remelted dust. One component displaying an Al-Ir correlation is identified as Allende-type white aggregates. The other components are a material chemically similar to the present matrix and sulfides-plus-metal material. Abundances of the REE (rare earth elements) were measured in ‘ordinary’ Allende chondrules and were 50% higher than REE abundances in Mokoia chondrules; REE abundances in Ca-Al rich chondrules were similar to REE abundances in Ca-rich white aggregates.     

Multi-Collector SIMS Determination of Trace Lanthanides in Zircon

A method is presented for the determination of rare earth elements (REE) in zircon (ZrSiO₄) using a multi-collector equipped ion-microprobe operating at moderately high mass resolution (M/ΔM ˜ 3900). The low abundance light REE (La-Eu) were measured simultaneously in six ion counting electron multipliers, reducing analytical time to less than half of that in a monocollection routine. Effective mass filtering, moderate energy filtering and careful set up of detector parameters in order to minimise background counts, yielded a highly coherent set of analyses from the 91500 zircon reference sample.     

赣南新元古代变质岩稀土矿物及其地球化学特征

近年来赣南地区首次报道了变质岩离子吸附型稀土矿床的发现,为离子吸附型稀土的找矿提供了新思路。赣南地区新元古代变质岩大面积分布,风化壳也广泛发育。文章对30件稀土元素含量(300×10~(-6))高的变质岩矿物样品进行了详细的电子探针分析,旨在查明赣南新元古代不同类型变质岩中的稀土矿物种类及特征,探讨其成因、对全岩稀土元素含量的贡献以及离子吸附型稀土元素的成矿潜力。研究表明,区域上变质岩可大致分为6类,分别是变质凝灰岩类、板岩类、千枚岩类、片岩类、变砂岩类和变粒岩类,不同类型变质岩的稀土矿物组合不同,除了普遍存在的、难风化的独居石、磷钇矿和锆石外,部分岩性中出现易风化的褐帘石、含稀土元素绿泥石和含稀土元素金红石,及表生的水磷酸盐和磷铝酸盐等矿物。这些富稀土矿物贡献了全岩中大部分稀土元素,且部分矿物成因与后期流体作用相关,为成矿提供了良好的条件。文章总结分析认为,赣南地区广泛分布的变质岩中,片岩类、变砂岩类和变质凝灰岩类均具有相对易风化的稀土矿物组合,尤其变质凝灰岩类和变砂岩类,能为离子吸附型稀土成矿提供充足的物质来源,具有可观的离子吸附型稀土成矿潜力。     

Accurate Measurement of Rare Earth Elements by ICP‐MS after Ion‐Exchange Separation: Application to Ultra‐Depleted Samples

This study reports precise and accurate data for rare earth elements (REE) measured on eight geological reference materials, five enriched in REE (BE‐N, BHVO‐2, BR, BR‐24 and RGM‐1) and three very depleted in REE (BIR‐1, UB‐N and DTS‐2). Data were acquired by quadrupole ICP‐MS after isolation of the REE using an ion‐exchange chromatography procedure. All the measured REE abundances were similar within ≈ 5% (10% for the most REE‐depleted sample DTS‐2) to the high‐quality measurements previously published in the literature. We also show that by using an internal Tm spike, the reproducibility of the data was improved to ～ 1%. Applying this technique to the analysis of ultra‐depleted rock samples (sub ng g^?1), we show that significant improvements were obtained relative to the routine trace element measurement method. The chondrite‐normalised patterns were smooth instead of displaying irregularities. Although the classical method gives excellent results on REE‐rich samples, we believe that our technique improves the precision and accuracy of measurements for highly REE‐depleted rocks.     

Rare earth elements in high-grade metamorphic rocks from the western Alps

A sequence of amphibolite to granulite facies metasedimentary and mafic metaigneous rocks from the western Italian Alps has been analysed for rare earth elements (REE). In this sequence, the metasedimentary granulites have probably been affected by a melting event while the metaigneous granulites remained unaffected. Metasedimentary granulites have a less fractionated chondrite-normalized REE pattern than equivalent amphibolite facies rocks. The granulites tend to have a higher content of heavy REE and lower abundances of light REE (LREE). The leucosomes of migmatitic granulites have lower REE content than the melanocratic bands and both these rock types have variable relative abundances of Eu. The mafic granulites have LREE enriched patterns while the amphibolites are slightly depleted in LREE. The differences between the mafic granulites and amphibolites are probably of pre-metamorphic origin.     

Rare earth element distributions among coexisting granulite facies minerals,Scourian complex,NW Scotland

The major rock-forming mineral phases (pyroxenes, plagioclase, garnet, hornblende) of a suite of granulite-facies gneisses from the Scourian complex, NW Scotland, have been analyzed for their rare earth element (REE) content. Although host rock compositions range from felsic to ultramafic, REE abundances and patterns for each mineral group show only limited variation. The REEs exhibit regular and consistent distribution patterns for each mineral which suggest, together with major element and textural considerations, that the observed distribution coefficients approach equilibrium. Total REE content follows the sequence hornblende>clinopyroxene>garnet>plagioclase >orthopyroxene and mass balance calculations show that even in the felsic gneisses>60% of the REEs reside in the major rock-forming minerals. Comparisons of both relative REE abundances and distribution coefficients with those in other rock types reveal a striking resemblance with patterns observed in mineral-liquid pairs of dacitic rocks. These similarities may have arisen during a partial melting episode in which granite-granodiorite melts were generated and removed from the Scourian complex; leaving a residuum which is severely depleted in the incompatible elements, including the REEs.     

Rare earth element distributions in some Precambrian rocks and their phyllosilicates,Numedal, Norway

Mass spectrometric analyses for rare earth elements (REE) have been carried out on some Precambrian mica schists, gneisses and granites from the Precambrian Numedal area, Norway and on their phyllosilicates. The rocks, which are metamorphosed in the upper greenschist to amphibolite facies, were originally partly sedimentary, partly magmatic.The total REE contents for rocks varies from 145 to 761 ppm. An average of 16 phyllosilicate samples gave 417 ppm REE (max. of 1809 ppm, min. of ca. 50 ppm). Coexisting light and dark phyllosilicates have similar abundances of REE. For the micas of high REE content most of the REE was extractable by rinsing with EDTA. The data thus support the possibility of an extensive adsorption of REE ions on micaceous minerals. The REE distribution patterns do not provide a clear distinction between the sedimentary and magmatic origin for the rocks examined.