A Geochemical Study of an REE-rich Carbonatite Dyke at Bayan Obo, Inner Mongolia, Northern China

An REE-rich carbonatite dyke was found in Dulahala, close to the Bayan Obo superlarge REE-Nb-Fe mineral deposit in Inner Mongolia, northern China. The REE content in the dyke varies greatly, from 1% up to 20% (wt), which might constitute rich REE ores. Light REEs in the carbonatite are enriched and highly fractionated relative to heavy REEs and there is no Eu anomaly. The REE and trace element distribution patterns of the carbonatite are identical to those of fine-grained dolomite marble which is the host rock of the Bayan Obo REE-Nb-Fe superlarge mineral deposit. This indicates a petrogenetic linkage between the REE-rich carbonatite and the mineralizations in this region.     

Geochemical constraints on the genesis of the Bayan Obo Fe-Nb-REE deposit in Inner Mongolia, China

Trace element and isotopic compositions of carbonate from ore bodies, country rock which hosts the ore bodies (H8 dolomite), a carbonatite dyke exposed in Dulahala near Bayan Obo, and rare earth element (REE)-rich dolomite in Bayan Obo have been determined to understand the genesis of the Bayan Obo Fe-Nb-REE ore deposit, the world’s largest resource of REE. The REE and trace element distribution patterns of samples from the REE-rich carbonatite dykes are identical to those of mineralized carbonate rocks, indicating a genetic linkage between the REE-rich carbonatite and mineralization in this region. By contrast, carbon and oxygen isotopes in the mineralized carbonate varied significantly, δ¹³C = −7.98‰ to −1.12‰, δ¹⁸O = 8.60-25.69‰, which are distinctively different from those in mantle-derived carbonatite. Abnormal isotopic fractionations between dolomite and calcite suggest that these two minerals are in disequilibrium in the carbonatite dyke, ore bodies, and H8 marble from Bayan Obo. This isotopic characteristic is also found in mineralized sedimentary marine micrite from Heinaobao, ∼25 km southeast of the Bayan Obo Fe-Nb-REE ore deposit. These facts imply that the carbonate minerals in the Bayan Obo deposit have resulted from sedimentary carbonate rocks being metasomatised by mantle-derived fluids, likely derived from a REE-enriched carbonatitic magma. The initial Nd isotope values of ore bodies and carbonatite dykes are identical, indicating that ore bodies, carbonatite dykes and veins may have a similar REE source.     

Geochemical characteristics of the Bayan Obo giant REE–Nb–Fe deposit: Constraints on its genesis

Geochemical characteristics of different dolomites in the Bayan Obo giant REE–Nb–Fe deposit in Inner Mongolia have been studied. Intensively REE-mineralized dolomites (total REE over 800 ppm) show similar geochemical characteristics to associated carbonatite dykes, with Ba, Th, REE enrichments and Sr, Nb, Ti, Cu depletions, which is different from those of dolomites in the deposit with low REE contents (total REE less than 800 ppm). The low REE dolomites display some transitional characteristics between carbonatite dyke and sedimentary carbonate, with La depletion and Nb enrichment. This indicates that the genesis of the REE-mineralized dolomites might be related to both carbonatite magma and sedimentary carbonates. Sulfur isotope data indicates two sulfur sources, a mantle source (δ³⁴S c.a. 0‰) and seawater (δ³⁴S c.a. +25‰). It is proposed that mineralized dolomites in the Bayan Obo giant REE–Nb–Fe deposit are the product of sedimentary carbonate hydrothermally metasomatised by carbonatite magma and/or associated fluids. These dolomites formed the large-scale rare earth mineralization in the unique Bayan Obo REE–Nb–Fe deposit.     

内蒙古白云鄂博矿床的稀土矿化时代与期次

内蒙古白云鄂博REE-Fe-Nb矿床是世界罕见的超大型多金属矿床, 但矿床成因一直没有解决, 而年代学研究是解决矿床成因的基础。本文结合矿床地质特征, 系统地分析了前人的年代学研究成果, 并对白云鄂博矿床的Sm-Nd同位素体系进行了深入的分析和讨论。结果表明, 白云鄂博稀土的成矿时代约为1.3 Ga, 与碳酸岩墙的形成时间一致, 成矿物质来源于地幔。加里东期的热事件(约0.44 Ga)导致了白云鄂博矿床晚期稀土矿脉的形成和原有矿体中部分稀土矿物的重结晶, 但成矿物质主要来源于矿体内部的稀土再循环, 外源物质的贡献不明显。约1.3 Ga到约0.44 Ga间的一系列中间年龄为后期热扰动的结果, 并不代表成矿事件。简言之, 白云鄂博矿床只在中元古代发生过一次实质性的稀土矿化作用, 地幔是稀土物质的单一源区。     

Late Archaean mantle metasomatism below eastern Indian craton: Evidence from trace elements,REE geochemistry and Sr—Nd—O isotope systematics of ultramafic dykes

Trace, rare earth elements (REE), Rb-Sr, Sm-Nd and O isotope studies have been carried out on ultramafic (harzburgite and lherzolite) dykes belonging to the newer dolerite dyke swarms of eastern Indian craton. The dyke swarms were earlier considered to be the youngest mafic magmatic activity in this region having ages not older than middle to late Proterozoic. The study indicates that the ultramafic members of these swarms are in fact of late Archaean age (Rb-Sr isochron age 2613 ± 177 Ma, Sri ∼ 0.702 ± 0.004) which attests that out of all the cratonic blocks of India, eastern Indian craton experienced earliest stabilization event. Primitive mantle normalized trace element plots of these dykes display enrichment in large ion lithophile elements (LILE), pronounced Ba, Nb and Sr depletions but very high concentrations of Cr and Ni. Chondrite normalised REE plots exhibit light REE (LREE) enrichment with nearly flat heavy REE (HREE; (ΣHREE)_N ∼ 2–3 times chondrite, (Gd/Yb)_N ∼ 1). The ε^Nd(t) values vary from +1.23 to -3.27 whereas δ¹⁸O values vary from +3.16‰ to +5.29‰ (average +3.97‰±0.75‰) which is lighter than the average mantle value. Isotopic, trace and REE data together indicate that during 2.6 Ga the nearly primitive mantle below the eastern Indian Craton was metasomatised by the fluid (± silicate melt) coming out from the subducting early crust resulting in LILE and LREE enriched, Nb depleted, variable ε^Nd, low Sr_i(0.702) and low δ¹⁸O bearing EMI type mantle. Magmatic blobs of this metasomatised mantle were subsequently emplaced in deeper levels of the granitic crust which possibly originated due to the same thermal pulse.     

http://www.sciencedirect.com/science/article/pii/S1674987110000125

<正>Carbonatites are commonly related to the accumulation of economically valuable substances such as REE.Cu,and P.The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years.Worldwide,the rocks characteristically display more geochemical enrichments in Ba,Sr and REE than sedimentary carbonate rocks.However,carbonatite's geochemical features are disputed because of secondary mineral effects.Rock-forming carbonates from carbonatites at Qinling.Panxi region,and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns.They are characterized by a Sr content more than 10 times higher than that of secondary carbonates.The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance,indicating that they are of igneous origin.Some carbonates in Chinese carbonatites show REE(especially HREE) contents and distribution patterns similar to those of the whole rocks.These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and Ir relative to high-Si extrusive carbonatite.This indicates that most intrusive carbonatites may be carbonate cumulates.Maoniuping and Daluxiang in Panxi region are large REE deposits.Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite.The fiuorite in Maoniuping has Sr and Nd isotopes similar to carbonatite.The Daluxiang fiuorite shows Sr and REE compositions different from those in Maoniuping.The difference is reflected by both the carbonatites and rock-forming carbonates,indicating that REE mineralization is related to carbonatites.The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE.The carbonatite-derived fluid has interacted with wallrock to form REE ore veins.The amount of carbonatite dykes occurring near the Bayan Obo orebodies may support the same mineralization model,i.e.that fluids evolved from the carbonatite dykes reacted with H8 dolomite marble,and thus the different REE and isotope compositions of coarse- and fine-grained dolomite may be related to reaction processes.     

Integrated U–Pb and Sm–Nd geochronology for a REE-rich carbonatite dyke at the giant Bayan Obo REE deposit,Northern China

The Bayan Obo deposit in North China contains the largest rare-earth element (REE) resources in the world, but its forming time remains controversial. Nearly one hundred carbonatite dykes occur around the Bayan Obo deposit, including dolomite, calcite and calcite–dolomite carbonatite varieties. Zircons from a REE-rich carbonatite dyke and wallrock quartz conglomerate at Bayan Obo have been analyzed for U–Pb to determine the age of the dyke. Zircon from the carbonatite dyke, analyzed by conventional isotope dilution thermal ionization mass spectrometry (ID-TIMS), yielded an upper intercept age of 1417 ± 19 Ma. This age is confirmed by SHRIMP U–Pb analysis of zircon from the same carbonatite dyke, which gave a ²⁰⁷Pb/²⁰⁶Pb weighted mean age of 1418 ± 29 Ma. In situ Nd isotope measurements of monazite collected from the carbonatite dyke gave an isochron age of 1275 ± 87 Ma. These results demonstrate that the dyke intruded ~ 1400 Ma. In view of predecessor's results, it is clarified that the REE mineralization at Bayan Obo occurred at ca. 1400 Ma, consistent with the timing of carbonatite dyke intrusion in the region. The youngest detrital zircons from the quartz conglomerate yielded a ²⁰⁷Pb/²⁰⁶Pb weighted mean age of 1941 ± 7 Ma using LA ICP-MS U–Pb method. Detrital zircons in the carbonatite dyke also gave a mean apparent age of 1932 ± 3 Ma using ID-TIMS U–Pb method and 1914 ± 14 Ma using SHRIMP U–Pb method. These ages constrain the beginning active time of the Zha'ertai–Bayan Obo rift in the northern margin of the North China Craton after ~ 1900 Ma.     

Carbonatite dykes at bayan Obo,inner Mongolia,China

Summary Calcite-rich dykes occur in the thrust fold belt near the Bayan Obo rare earth element (REE) deposit. They cut a thrust inlier of granitic migmatite within folded Bayan Obo Group sediments of Proterozoic age. Cathodoluminescence, X-ray fluorescence and microprobe studies show that the rock is a calcite carbonatite with Sr-Mn-bearing calcite, magnesio-riebeckite, apatite, pyrochlore, K-feldspar and biotite. One dyke was chosen for detailed analysis. Its margin is strongly REE-mineralized with much monazite developed adjacent to zoned apatite. Secondary alteration is marked by the introduction of Fe and Mn. The adjacent migmatite is fenitized to a magnesio-riebeckite-albite rock. The sedimentary dolomite of the Bayan Obo Group is composed mainly of Mn-Sr-RE-hearing ferroan dolomite and contains bands of opaque grains, apatite, monazite, fluorite and taeniolite. Many trace element and isotope similarities between the carbonatite dyke and the sedimentary dolomite are revealed, and the evidence supports the possibility that the dolomite is a dolomitized carbonatite tuff. The Bayan Obo REE mineralization also shows geochemical similarities with the mineralization seen in the carbonatites, and a possible genetic connection is presented.

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Die Karbonatit-Gänge von Bayan Obo, Innere Mongolei, China

Zusammenfassung Kalzit-reiche Gänge kommen im Faltengürtel in der Nähe der Seltenen-Erd-Lagerstätte Bayan Obo vor. Es handelt sich um hellbräunliche, 1–2 m mächtige Gänge, die migmatitische Orthogneise von granitischer Zusammensetzung innerhalb der gefalteten Sedimente der Bayan Obo Gruppe durchsetzen. Chemische Daten, die auf Kathoden-Lumineszenz, Röntgen-Fluoreszenz und Mikrosondenuntersuchungen beruhen, zeigen, daß es sich hier um einen Kalzit-KazhooudimdSr-Mo-führeodem Kalzit, Magnesio-Riebeckit Apatit, Pyrochlor Alkalifelds und Biotit handelt. Einer dieser Gänge wurde für eine eingehende Untersuchung ausgewählt. Seine randlichen Partien sind stark mit SEE mineralisiert, und viel Monazit kommt in der Nähe von zonar gebautem Apatit vor. Sekundäre Umwandlung wird durch die Zufuhr von Fe und Mn markiert. Der benachbarte Migmatit ist fenitisiert und dadurch in ein Magnesio-Riebeckit-Gestein umgewandelt. Der sedimentäre Dolomit der Bayan-Obo-Gruppe besteht hauptsächlich aus Mn-Sr-SE-führenden eisenhaltigen Dolomit und enthält Lagen von opaken Mineralen, Apatit, Monazit, Fluorit und Taeniolit. Karbonatitgänge und der sedimentäre Dolomit zeigen Ähnlichkeiten, was den Spurenelementgehalt und die isotopische Zusammensetzung betrifft. Diese Daten weisen auf die Möglichkeit hin, daß der Dolomit ein dolomitisiert Karbonatit-Tuff ist. Die SEE-Vererzung von Bayan Obo zeigt auch geochemische Ähnlichkeiten mit der Vererzung der Karbonatite, und ein möglicher genetischer Zusammenhang wird diskutiert.

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With 16 Figures     

四川冕宁包子山稀土矿床富Sr碳酸岩的发现及意义

全球范围内出露的碳酸岩大多为钙质、镁质、铁质碳酸岩,少量为钠质和硅质碳酸岩,极少有富Sr碳酸岩的报道,其岩石成因、资源意义及对碳酸岩岩浆演化的指示意义尚不清楚。本次在四川省牦牛坪稀土矿区南部包子山稀土矿床的露天采坑中发现了超级富Sr的碳酸岩,其呈不规则的脉状侵入到构造角砾岩中。岩石呈紫色-淡紫色,微晶-斑状结构,斑晶主要为萤石,基质主要为菱锶矿、方解石、氟碳铈矿、氟碳钙铈矿、金云母、重晶石并含少量的金属硫化物和氧化物。全岩的微量元素分析表明,其稀土元素总量(∑REE)达3.5%～6.1%,Sr含量达19.0%～27.7%,已超过稀土矿床和锶矿床的工业品位要求。岩石中的中、重稀土元素含量占稀土元素总量的1.14%～1.77%,一些高价值稀土元素含量较高,如Pr(939×10~(-6)～1399×10~(-6))、Nd(2783×10~(-6)～3937×10~(-6))、Gd(237×10~(-6)～320×10~(-6)),因此除轻稀土元素外,中、重稀土和锶元素也具有重要的资源意义。岩石强烈富集REE、Sr、Ba,而明显亏损P、Nb、Ta、Zr、Hf元素,可能与岩浆演化过程中锆石和其它基性矿物的结晶分离有关。全岩的Sr-Nd同位素组成与牦牛坪、里庄稀土矿床的碳酸岩相似,表明它们为同源岩浆产物。笔者认为,富Sr的碳酸岩代表了碳酸岩岩浆演化晚期的产物,REE、Sr、Ba、F和S元素均在岩浆演化晚期的碳酸岩中高度富集。碳酸岩岩浆超浅成侵位至构造角砾岩中,并与下渗的大气水相遇导致岩浆的淬冷和微晶-斑状结构的形成。早期基性矿物(如霓辉石、黑云母)及碳酸盐矿物(如方解石、白云石等)的结晶分离是造成晚期碳酸岩中稀土元素富集的重要原因。富Sr碳酸岩中石英斑晶的发现和其较低的SiO_2含量表明碳酸岩岩浆演化晚期可能是硅饱和的,且这种岩浆具有很低的SiO_2溶解能力。以菱锶矿(体积分数 50%)为主要碳酸盐矿物的稀土碳酸岩可能代表了一种新的碳酸岩类型,明显不同于已知的钙质、镁质、铁质和钠质碳酸岩。     

Is the Bayan Obo ore deposit a micrite mound? A comparison with the Sailinhudong micrite mound

The origin of the Bayan Obo ore deposit, the largest REE deposit in the world, has long been debated and various hypotheses have been proposed. Among them is that the Bayan Obo ore deposit is correlated with and has the same origin as the Sailinhudong micrite mound in the southern limb of the Bayan Obo synclinorium. To test this model, the Bayan Obo ore deposit and the Sailinhudong micrite mound are systematically compared for their geological features, elemental geochemistry, and C, O, and Mg isotopic geochemistry. We show that the Bayan Obo ore deposit and the Sailinhudong micrite mound are both calcareous, lens-like in shape, lack bedding features, and are both hosted in a sedimentary formation that consists of clastic sediments and carbonates, unconformably overlying the Archaean–Palaeoproterozoic crystalline basement. However, their geochemical characteristics differ markedly. Compared with the Sailinhudong micrite carbonates, the Bayan Obo ore-hosting dolomite marbles are strongly enriched in LREEs, Ba, Th, Nb, Pb, and Sr, and have very different (PAAS)-normalized REE patterns. Sailinhudong micrite carbonates have higher δ¹³C_PDB and δ¹⁸O_SMOW values, falling into the typical sedimentary field, but the Bayan Obo ore-hosting dolomites are isotopically intermediate between primary igneous carbonatite and typical sedimentary limestone. The δ²⁶ Mg values of the Sailinhudong micrite carbonates are lighter than those of normal Mesoproterozoic sedimentary dolostone, while those of the Bayan Obo ore-hosting dolomite marble are isotopically heavier, similar to δ²⁶ Mg of mantle xenoliths and Bayan Obo intrusive carbonatite. We conclude that the Bayan Obo ore deposit is not correlated with the Sailinhudong micrite mound; it is neither a micrite mound nor an altered micrite mound.     

Immiscible separation of metalliferous Fe/ Ti-oxide melts from fractionating alkali basalt: P-T-f O2 conditions and two-liquid elemental partitioning

Globules of iron-dominated (59–69 wt% FeO_tot) and titanium-dominated (43.5 wt% TiO₂) oxide melts have been detected in igneous xenoliths from Pliocene-to-Pleistocene alkali basalts of the Western Carpathians. Fluid inclusion and mineral composition data indicate immiscible separation of the high-iron-oxide melt (HIM) at magmatic temperatures. The HIM separation occurred during clinopyroxene (augite) accumulation in an alkali trachybasalt and continued during crystallization of amphibole (kaersutite) and K-feldspar (anorthoclase), the latter coexisting with trachyte and alkalic rhyolite residual melts. Some HIM was also expelled from sub-alkalic rhyolite (70–77% SiO₂), coexisting with An_27–45 plagioclase and quartz in granitic (tonalite-trondhjemite) xenoliths. Oxygen fugacities during HIM separation range from −1.4 to +0.6 log units around the QFM buffer. A close genetic relationship between HIM-hosted xenoliths and mantle-derived basaltic magma is documented by mineral ¹⁸O values ranging from 4.9 to 5.9‰ V-SMOW. δD values of gabbroic kaersutite between −61 and −86‰ V-SMOW are in agreement with a presumed primary magmatic water source. Most trace elements, except Li, Rb and Cs, have preferentially partitioned into the HIM. The HIM/Si-melt partition coefficients for transition elements (Sc, V, Cr, Co, Ni) and base metals (Zn, Cu, Mo) are between 2–160, resulting in extreme enrichment in the HIM. La and Ce also concentrate in the silicic melt, whereas Tb-Tm in the HIM. Hence, the immiscible separation causes REE fractionation and produces residual silicic melt enriched in LREE and depleted in HREE. The weak fractionation among Tb-Tm and Yb, Lu can be attributed to recurrent extraction of the HIM from the magmatic system, while flat HREE chondrite-normalized patterns are interpreted to indicate no or little loss of the HIM. Received: 30 September 1997 / Accepted: 23 March 1998     

A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

Oxygen isotope composition of phenocrysts from Tristan da Cunha and Gough Island lavas: variation with fractional crystallization and evidence for assimilation

We have measured the δ¹⁸O values of the major phenocrysts (olivine, clinopyroxene and plagioclase) present in lavas from Tristan da Cunha and Gough Island. These islands, which result from the same mantle plume, have enriched radiogenic isotope ratios and are, therefore, prime candidates for an oxygen isotope signature that is distinct from that of MORB. Consistent differences between the δ¹⁸O values of olivine, pyroxene and feldspar in the Gough lavas show that the phenocrysts in the mafic Gough Island lavas are in oxygen isotope equilibrium. The olivines in lavas with SiO₂ <50 wt% have a mean δ¹⁸O value of 5.19‰, consistent with crystallization from a magma having the same oxygen isotope composition as MORB. Phenocrysts in all the Gough lavas show a systematic increase in δ¹⁸O value as silica content increases, which is consistent with closed-system fractional crystallization. The lack of enrichment in δ¹⁸O of the Gough magmas suggests that the mantle source contained <2% recycled sediment. In contrast, the Tristan lavas with SiO₂ >48 wt% contain phenocrysts which have δ¹⁸O values that are systematically ∼0.3‰ lower than their counterparts from Gough. We suggest that the parental mafic Tristan magmas were contaminated by material from the volcanic edifice that acquired low δ¹⁸O values by interaction with water at high temperatures. The highly porphyritic SiO₂-poor lavas show a negative correlation between olivine δ¹⁸O value and whole-rock silica content rather than the expected positive correlation. The minimum δ¹⁸O value occurs at an SiO₂ content of about 45 wt%. Below 45 wt% SiO₂, magmas evolved via a combination of assimilation, fractionational crystallization and crystal accumulation; above 45 wt% SiO₂, magmas appeared to have evolved via closed-system fractional crystallization. Received: 23 November 1998 / Accepted: 27 September 1999     

Melt/rock interaction in remains of refertilized Archean lithospheric mantle in Jiaodong Peninsula, North China Craton: Li isotopic evidence

Li contents and its isotopes of minerals in mantle peridotite xenoliths from late Cretaceous mafic dikes, analyzed in situ by Cameca IMS-1280, reveal the existence of melt/rock interaction in remains of refertilized Archean lithospheric mantle in Qingdao, Jiaodong Peninsula, North China Craton. Two groups of peridotites exist, i.e., low-Mg# lherzolite and high-Mg# harzburgites. The low-Mg# lherzolite has a relatively homogeneous Li concentration (ol: 2.01–2.11 ppm; opx: 1.77–1.88 ppm; cpx: 1.75–1.93 ppm) and Li isotopic composition (δ⁷Li in ol: 4.2–7.6‰; in opx: 6.0–8.3‰; in cpx: 5.3–8.4‰). The similarity in δ⁷Li value to the fresh MORB provides further evidence for the argument that the low-Mg# lherzolite could be the fragment of the newly accreted lithospheric mantle. The high-Mg# harzburgites have heterogeneous Li abundances (ol: 0.83–2.09 ppm; opx: 0.92–1.94 ppm; cpx: 1.12–4.89 ppm) and Li isotopic compositions (δ⁷Li in ol: −0.5 to +11.5‰; in opx: −6.2 to +11.1‰; in cpx: −34.3 to +10.1‰), showing strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The cores of most minerals in these high-Mg# harzburgites have relatively homogeneous δ⁷Li values, which are higher than those of fresh MORB, but similar to those previously reported for arc lavas. These harzburgites have enriched trace elemental and Sr–Nd isotopic compositions. These observations indicate that in the early Mesozoic the lithospheric mantle beneath the southeastern North China Craton was similar to that in arc settings, which is metasomatized by subducted crustal materials. Extremely low δ⁷Li preserved in cpxs requires diffusive fractionation of Li isotopes from later-stage melt into the minerals. Thus, the Li data provide further evidence that the Archean refractory lithospheric mantle represented by the high-Mg# harzburgites was refertilized through melt/rock interaction and transformed to the Mesozoic less refractory and incompatible element and Sr–Nd isotopes enriched lithospheric mantle.     

白云鄂博碳酸岩型REE-Nb-Fe矿床——一个罕见的中元古代破火山机构成岩成矿实例

白云鄂博碳酸岩型REE-Nb-Fe矿床是世界上最大的稀土矿床。稀土矿石产于整个白云石碳酸岩体和部分脉状碳酸岩中。对比世界上20余个火成碳酸岩地区的特征后发现,白云鄂博地区完全具备国外火成碳酸岩区的地质特征。在岩石、矿石组合上,本区也发育一套碳酸岩+超基性岩+碱性基性岩(含基性熔岩)+碱性岩+稀土矿石+铁矿石组合;在矿物组合上,以白云石为主,方解石次之,伴生一套碱性闪石、长石、霓石、磷灰石、萤石、磁铁矿、稀土矿物组合;在全岩化学成分、微量元素、稀土元素和Sr、Nd、Pb、C、O同位素上,这些岩石具有一定的亲缘关系,有着共同的来源;在岩体的形态与岩石组构上,它们以岩席、岩筒和脉岩的形式出现,并发育有强烈的熔离作用与流动构造;在区域构造上,发育隐伏穹窿构造、岩筒构造和巨型断裂汇聚构造。综合分析上述特征表明:白云鄂博地区具有中元古代破火山机构的痕迹,赋矿白云石碳酸岩体则是顺层侵入的火成碳酸岩体,东矿、主矿可能是一个火山颈构造控矿,而赋矿白云石碳酸岩体西南侧的苏木图矿床则是隐伏岩筒构造控矿。     

Sr and Nd isotope data of apatite,calcite and dolomite as indicators of source,and the relationships of phoscorites and carbonatites from the Kovdor massif,Kola peninsula,Russia

A detailed Sr−Nd isotopic study of primary apatite, calcite and dolomite from phoscorites and carbonatites of the Kovdor massif (380 Ma), Kola peninsula, Russia, reveals a complicated evolutionary history. At least six types of phoscorites and five types of carbonatite have been identified from Kovdor by previous investigators based on relative ages and their major and accessory minerals. Isotopic data from apatite define at least two distinct groups of phoscorite and carbonatite. Apatite from the earlier phoscorites and carbonatites (group 1) are characterized by relatively low⁸⁷Sr/⁸⁶Sr (0.70330–0.70349) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51230–0.51240) with F=2.01–2.23 wt%, Sr=2185–2975 ppm, Nd=275–660 ppm and Sm=31.7–96.2 ppm. Apatite from the second group has higher⁸⁷Sr/⁸⁶Sr (0.70350–0.70363) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51240–0.51247) and higher F (2.63–3.16 wt%), Sr (4790–7500 ppm), Nd (457–1074 ppm) and Sm (68.7–147.6 ppm) contents. This group corresponds to the later phoscorites and carbonatites. One apatite sample from a carbonatite from the earlier group fits into neither of the two groups and is characterized by the highest initial⁸⁷Sr/⁸⁶Sr (0.70385) and lowest¹⁴³Nd/¹⁴⁴Nd (0.51229) of any of the apatites. Within both groups initial⁸⁷Sr/⁸⁶Sr and¹⁴³Nd/¹⁴⁴Nd ratios show negative correlations. Strontium isotope data from coexisting calcite and dolomite support the findings from the apatite study. The Sr and Nd isotopic similarities between carbonatites and phoscorites indicate a genetic relationship between the two rock types. Wide variations in Sr and Nd isotopic composition within some of the earlier carbonatites indicate several distinct intrusive phases. Oxygen isotopic data from calcite and dolomite (δ¹⁸O=+7.2 to +7.7‰ SMOW) indicate the absence of any low-temerature secondary processes in phoscorites and carbonatites, and are consistent with a mantle origin for their parental melts. Apatite data from both groups of phoscorite plot in the depleted quadrant of an ε_Nd versus ε_Sr diagram. Data for the earlier group lie along the Kola Carbonatite Line (KCL) as defined by Kramm (1993) and data from the later group plot above the KCL. The evolution of the phoscorites and carbonatites cannot be explained by simple magmatic differentiation assuming closed system conditions. The Sr−Nd data can best be explained by the mixing of three components. Two of these are similar to the end-members that define the Kola Carbonatite Line and these were involved in the genesis of the early phoscorites and carbonatites. An additional component is needed to explain the isotopic characteristics of the later group. Our study shows that apatite from rocks of different mineralogy and age is ideal for placing constraints on mantle sources and for monitoring the Sr−Nd evolution of carbonatites. Editorial responsibility: W. Schreyer     

白云鄂博铁、铌、稀土矿床:研究进展、存在问题和新认识

白云鄂博是世界第一大稀土元素矿床,其稀土元素资源量占世界目前已知稀土元素资源总量的三分之二以上,具有重要的经济和战略地位。白云鄂博自1927年发现至今已有92年,对其的开发和研究历史悠久,在赋矿碳酸岩的成因、成矿年代、稀土矿物学等方面取得了一系列重要进展,为碳酸岩型稀土元素成矿理论发展做出了突出贡献。由于矿床经历了成矿后复杂的构造变形和热液蚀变,致使其地质、地球化学特征复杂,学界对其成因和成矿过程一直存在不同认识,对成矿碳酸岩的岩浆演化、稀土元素迁移与富集机理等方面的研究也相对薄弱。笔者最新研究表明,矿区过去被认为是下白云鄂博群的H1、H2、H9岩石单元并非沉积变质岩或变质火山岩,而应为岩浆侵入成因,矿区其他岩石单元(H3～H7)的成因也值得商榷。H9岩石单元中的黑云母岩(前人称为黑云母板岩)和富含黑云母的碳酸岩(前人称为暗色板岩)为成矿碳酸岩的一部分,是碳酸岩不同岩相带的表现。黑云母岩和富黑云母碳酸岩相对于含矿碳酸岩具有相对低的稀土元素含量和轻、重稀土元素比值,表明岩浆演化可能对稀土元素的富集和分异具有重要贡献。矿区主要岩石单元成因的新认识不仅为矿床成因、成矿背景研究提供了新的依据,同时也为研究区域构造演化、正确厘定矿区构造式样和指导矿区深部和外围找矿提供了新的思路。     

300 Million years of episodic hydrothermal activity: stable isotope evidence from hydrothermal rocks of the Eastern Iberian Central System

The Eastern Iberian Central System has abundant ore showings hosted by a wide variety of hydrothermal rocks; they include Sn-W, Fe and Zn-(W) calcic and magnesian skarns, shear zone- and episyenite-hosted Cu-Zn-Sn-W orebodies, Cu-W-Sn greisens and W-(Sn), base metal and fluorite-barite veins. Systematic dating and fluid inclusion studies show that they can be grouped into several hydrothermal episodes related with the waning Variscan orogeny. The first event was at about 295 Ma followed by younger pulses associated with Early Alpine rifting and extension and dated near 277, 150 and 100 to 20 Ma, respectively (events II–IV). The δ¹⁸O-δD and δ³⁴S studies of hydrothermal rocks have elucidated the hydrological evolution of these systems. The event I fluids are of mixed origin. They are metamorphic fluids (H₂O-CO₂-CH₄-NaCl; δ¹⁸O=4.7 to 9.3‰; δD ab.−34‰) related to W-(Sn) veins and modified meteoric waters in the deep magnesian Sn-W skarns (H₂O-NaCl, 4.5–6.4 wt% NaCl eq.; δ¹⁸O=7.3–7.8‰; δD=−77 to −74‰) and epizonal shallow calcic Zn-(W) and Fe skarns (H₂O-NaCl, <8 wt% NaCl eq.; δ¹⁸O=−0.4 to 3.4‰; δD=−75 to −58‰). They were probably formed by local hydrothermal cells that were spatially and temporally related to the youngest Variscan granites, the metals precipitating by fluid unmixing and fluid-rock reactions. The minor influence of magmatic fluids confirms that the intrusion of these granites was essentially water-undersaturated, as most of the hydrothermal fluids were external to the igneous rocks. The fluids involved in the younger hydrothermal systems (events II–III) are very similar. The waters involved in the formation of episyenites, chlorite-rich greisens, retrograde skarns and phyllic and chlorite-rich alterations in the shear zones show no major chemical or isotopic differences. Interaction of the hydrothermal fluids with the host rocks was the main mechanism of ore formation. The composition (H₂O-NaCl fluids with original salinities below 6.2 wt% NaCl eq.) and the δ¹⁸O (−4.6 to 6.3‰) and δD (−51 to −40‰) values are consistent with a meteoric origin, with a δ¹⁸O-shift caused by the interaction with the, mostly igneous, host rocks. These fluids circulated within regional-scale convective cells and were then channelled along major crustal discontinuities. In these shear zones the more easily altered minerals such as feldspars, actinolite and chlorite had their δ¹⁸O signatures overprinted by low temperature younger events while the quartz inherited the original signature. In the shallower portions of the hydrothermal systems, basement-cover fluorite-barite-base metal veins formed by mixing of these deep fluids with downwards percolating brines. These brines are also interpreted as of meteoric origin (δ¹⁸O< ≈ −4‰; δD=−65 to −36‰) that leached the solutes (salinity >14 wt% NaCl eq.) from evaporites hosted in the post-Variscan sequence. The δD values are very similar to most of those recorded by Kelly and Rye in Panasqueira and confirm that the Upper Paleozoic meteoric waters in central Iberia had very negative δD values (≤−52‰) whereas those of Early Mesozoic age ranged between −65 and −36‰. Received: 9 June 1999 / Accepted: 19 January 2000     

Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

Trace element and Pb–B–Li isotope systematics of olivine-hosted melt inclusions: insights into source metasomatism beneath Stromboli (southern Italy)

We studied the elemental and isotopic (Pb, B and Li isotopes) composition of melt inclusions hosted in highly forsteritic (Fo_83–91) olivines that were collected from San Bartolo lava and pumice (ST79p, ST82p and ST531p) samples erupted by Stromboli in historical times. The studied melt inclusions have primitive calcalkaline to shoshonitic basaltic compositions. They cover a compositional range far wider than that exhibited by the whole-rocks and differ in key trace element ratios. San Bartolo melt inclusions are characterized by lower incompatible trace element abundances, higher ratios between fluid-mobile (B, Pb, U and LILE) and less fluid-mobile (REE, Th, HFSE) elements and lower La/Yb ratios relative to the pumice-hosted melt inclusions and pumiceous melts erupted during paroxysmal events. Trace elements, along with different Pb, B and Li isotopic signatures, attest to source heterogeneity on the small scale and provide new insights into subducted components beneath Stromboli. Results of a mixing model suggest that metasomatism of the mantle source of pumice-hosted melt inclusions was driven by solute-rich high-pressure fluids (<20%) expelled from the deep portion of the slab. Heterogeneous Pb isotopic composition together with light δ¹¹B (−8.6 to −13.7‰) and δ⁷Li (+2.3 to −1.7‰) indicates that high-pressure liquids were released in variable proportions from highly dehydrated metabasalts and metasediments. On the other hand, the elemental and isotopic (δ¹¹B ~ −1.9 to −5.9‰) composition of San Bartolo melt inclusions is better explained by the addition of a prevalent aqueous component (~2 to 4%) escaped at shallower depths from sediments and altered basaltic crust in almost equivalent proportions, with a smaller contribution by high-pressure fluids. Owing to the high-angle dip of the subducted cold Ionian slab, aqueous fluids and high-pressure fluids would rise through the mantle wedge and locally superimpose on each other, thus giving origin to variously metasomatized mantle domains.