The role of carbonate-fluoride melt immiscibility in shallow REE deposit evolution

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements(REE). Both carbonatites and nepheline syenite-fluorite-calcite veinlets are host to a previously unreported macroscale texture involving pseudo-graphic intergrowths of fluorite and calcite. The inclusions within calcite occur as either pure fluorite, with associated REE minerals within the surrounding calcite, or as mixed calcite-fluorite inclusions, with associated zirconosilicate minerals. Consideration of the nature of the texture, and the proportions of fluorite and calcite present(～29 and 71 mol%,respectively), indicates that these textures most likely formed either through the immiscible separation of carbonate and fluoride melts, or from cotectic crystallization of a carbonatefluoride melt. Laser ablation ICP-MS analyses show the pure fluorite inclusions to be depleted in REE relative to the calcite. A model is proposed, in which a carbonate-fluoride melt phase enriched in Zr and the REE, separated from a phonolitic melt, and then either unmixed or underwent cotectic crystallization to generate an REE-rich carbonate melt and an REE-poor fluoride phase. The separation of the fluoride phase(either solid or melt) may have contributed to the enrichment of the carbonate melt in REE, and ultimately its saturation with REE minerals. Previous data have suggested that carbonate melts separated from silicate melts are relatively depleted in the REE, and thus melt immiscibility cannot result in the formation of REE-enriched carbonatites. The observations presented here provide a mechanism by which this could occur, as under either model the textures imply initial separation of a mixed carbonate-fluoride melt from a silicate magma. The separation of an REEenriched carbonate-fluoride melt from phonolitic magma is a hitherto unrecognized mechanism for REE-enrichment in carbonatites, and may play an important role in the formation of shallow magmatic REE deposits.     

Petrogenetic processes in the ultramafic, alkaline and carbonatitic magmatism in the Kola Alkaline Province: A review

Igneous rocks of the Devonian Kola Alkaline Carbonatite Province (KACP) in NW Russia and eastern Finland can be classified into four groups: (a) primitive mantle-derived silica-undersaturated silicate magmas; (b) evolved alkaline and nepheline syenites; (c) cumulate rocks; (d) carbonatites and phoscorites, some of which may also be cumulates. There is no obvious age difference between these various groups, so all of the magma-types were formed at the same time in a relatively restricted area and must therefore be petrogenetically related. Both sodic and potassic varieties of primitive silicate magmas are present. On major element variation diagrams, the cumulate rocks plot as simple mixtures of their constituent minerals (olivine, clinopyroxene, calcite, etc). There are complete compositional trends between carbonatites, phoscorites and silicate cumulates, which suggests that many carbonatites and phoscorites are also cumulates. CaO / Al₂O₃ ratios for ultramafic and mafic silicate rocks in dykes and pipes range up to 5, indicating a very small degree of melting of a carbonated mantle at depth. Damkjernites appear to be transitional to carbonatites. Trace element modelling indicates that all the mafic silicate magmas are related to small degrees of melting of a metasomatised garnet peridotite source. Similarities of the REE patterns and initial Sr and Nd isotope compositions for ultramafic alkaline silicate rocks and carbonatites indicate that there is a strong relationship between the two magma-types. There is also a strong petrogenetic link between carbonatites, kimberlites and alkaline ultramafic lamprophyres. Fractional crystallisation of olivine, diopside, melilite and nepheline gave rise to the evolved nepheline syenites, and formed the ultramafic cumulates. All magmas in the KACP appear to have originated in a single event, possibly triggered by the arrival of hot material (mantle plume?) beneath the Archaean/Proterozoic lithosphere of the northern Baltic Shield that had been recently metasomatised. Melting of the carbonated garnet peridotite mantle formed a spectrum of magmas including carbonatite, damkjernite, melilitite, melanephelinite and ultramafic lamprophyre. Pockets of phlogopite metasomatised lithospheric mantle also melted to form potassic magmas including kimberlite. Depth of melting, degree of melting and presence of metasomatic phases are probably the major factors controlling the precise composition of the primary melts formed.     

Fluid inclusions in apatite from Jacupiranga calcite carbonatites: Evidence for a fluid-stratified carbonatite magma chamber

Carbonatites of the Jacupiranga alkaline–carbonatite complex in São Paulo State, Brazil, were used to investigate mineral–fluid interaction in a carbonatite magma chamber because apatite showed a marked discontinuity between primary fluid inclusion-rich cores and fluid inclusion-poor rims. Sylvite and burbankite, apatite, pyrite, chalcopyrite and ilmenite are the common phases occurring as trapped solids within primary fluid inclusions and reflect the general assemblage of the carbonatite. The apatite cores had higher Sr and REE concentrations than apatite rims, due to the presence of fluid inclusions into which these elements partitioned. A positive cerium anomaly was observed in both the core and rim of apatite crystals because oxidised Ce⁴⁺ partitioned into the magma. The combined evidence from apatite chemistry, fluid inclusion distribution and fluid composition was used to test the hypotheses that the limit of fluid inclusion occurrence within apatite crystals arises from: (1) generation of a separate fluid phase; (2) utilization of all available fluid during the first stage of crystallization; (3) removal of crystals from fluid-rich magma to fluid-poor magma; (4) an increase in the growth rate of apatite; or (5) escape of the fluids from the rim of the apatite after crystallization. The findings are consistent with fractionation and crystal settling of a carbonatite assemblage in a fluid-stratified magma chamber. Secondary fluid inclusions were trapped during a hydrothermal event that precipitated an assemblage of anhedral crystals: strontianite, carbocernaite, barytocalcite, barite and norsethite, pyrophanite, magnesian siderite and baddeleyite, ancylite-(Ce), monazite-(Ce) and allanite. The Sr- and REE-rich nature of the secondary assemblage, and lack of a positive cerium anomaly indicate that hydrothermal fluids have a similar source to the primary magma and are related to a later carbonatite intrusion.     

Primary magmas at Oldoinyo Lengai: The role of olivine melilitites

The paper describes olivine melilitites at Oldoinyo Lengai, Tanzania, and from tuff cones from the Tanzanian rift valley in the vicinity of Oldoinyo Lengai. Oldoinyo Lengai is the only active carbonatite volcano and is distinguished by its alkali-rich natrocarbonatites. Lengai is also unique for its extreme peralkaline silicate lavas related directly to the natrocarbonatites. Primitive olivine melilitites are, according to their Mg# and Ni, Cr contents, the only candidates in the Lengai area for primary melt compositions. Incompatible trace elements, including REE, constrain the melting process in their sub-lithospheric sources to very low degrees of partial melting in the garnet stability field. The strong peralkaline trend at Oldoinyo Lengai is already recognisable in these primary or near-primary melts. More evolved olivine melilitites, with Mg# < 60 allow the fractionation line in its major and trace element expressions to be followed. Nevertheless, a large compositional gap separates the olivine melilitites and olivine-poorer melilitites from the phonolites and nephelinites that form the bulk of the Lengai cone. These silicate lavas show a high degree of peralkalinity and are highly evolved with very low Mg, Ni and Cr. Prominent examples of the recent evolution are the combeite–wollastonite nephelinites that are unique for Lengai. In their Sr, Nd, and Pb isotope relationships the olivine melilitites define a distinct group with the most depleted Sr and Nd ratios and the most radiogenic Pb isotopes. They are closest to a supposed HIMU end member of the Lengai evolution, which is characterised by an extreme spread in isotopic ratios, explained as a mixing line between HIMU and EM1-like mantle components.     

Comparison of petrogenetic signatures between mantle-derived alkali silicate intrusives with and without associated carbonatite, Namibia

We compare the petrogenetic and chemical signatures of two alkali silicate suites from the Cretaceous Damaraland igneous province (Namibia), one with and one without associated carbonatite, in order to explore their differences in terms of magma source and evolution. The Etaneno complex occurs in close spatial proximity to the Kalkfeld bimodal carbonatite–alkali silicate complex, and is dominated by nepheline (ne)-monzosyenites and ne-bearing alkali feldspar syenites. The Etaneno samples have isotopic compositions of ⁸⁷Sr/⁸⁶Sr(i)=0.70462–0.70508 and Nd=−0.5 to −1.5, with the highest ⁸⁷Sr/⁸⁶Sr(i) and lowest Nd values observed in evolved samples. The magma differentiated via olivine, feldspar, clinopyroxene, and nepheline (ne) fractionation in a F-rich system, which fractionated Zr from Hf, and Y from Ho. Partly glassy, recrystallized inclusions in some samples are less evolved than their host rocks and contain a cumulate component (nepheline, plagioclase). The Kalkfeld ne-foidites (ijolites) and ne-syenites have ⁸⁷Sr/⁸⁶Sr(i)=0.70285–0.70592 and Nd=0.5 to 1.1. The isotope ratios show no consistent variation with rock composition, and they are in the same range as the associated carbonatites. The Kalkfeld silicate magma fractionated nepheline and alkali-feldspar in a CO₂-dominated, F- and Ca-poor system. As a result, the rocks display some major and trace element trends distinctly different from those of the Etaneno samples.

We suggest that the Etaneno and the Kalkfeld magmas represent different melt fractions of a heterogeneous mantle source, resulting in different compositions especially with respect to CO₂ contents of the primitive, parental magmas. In this scenario, the carbonated alkali silicate Kalkfeld parental melt contained a critical CO₂ concentration and underwent liquid separation of carbonate and silicate melt fractions at crustal depths. The resulting silicate melt fraction experienced a very different mode of differentiation than the carbonate-poor Etaneno parental magma. Thus, the Kalkfeld rocks are depleted in Ca and other divalent cations, as well as F, rare-earth elements (REE), Ba, and P relative to the Etaneno syenites. We interpret these differences to reflect the partitioning of these elements into the carbonate melt fraction during immiscible separation.     

牦牛坪稀土矿床碳酸岩Pb同位素地球化学

四川牦牛坪稀土矿床与稀土矿化时空密切共生的碳酸岩一正长岩碱性杂岩体的成岩时代为喜山期,碳酸岩呈脉状沿正长岩岩体中心侵入。两者具有相似的^206Pb／^204Pb和^208Pb／^204Pb比值,但碳酸岩^207Ph／^204Ph比值变化较大,且低于正长岩。这种差异并不能归因于地壳物质的混染作用,而是反映了地幔源区的特征。在Ph、Sr和Nd同位素图解中,矿区碳酸岩和正长岩显示低Ph,高Sr同位素的特征,部份碳酸岩Ph同位素落在MORB内,而Sr和Nd同位素明显不同于MORB,相对接近洋岛玄武岩的Ⅰ型富集地幔(EM1)。喜山期扬子板块呈楔形体插入龙门山地壳之中,受挤压的中下部地壳向前陆深处发生俯冲,并延伸至攀西裂谷顶部富集地幔体中,被交代的富集地幔经不同程度的和不连续的部份熔融作用形成碱性岩浆,整个演化过程导致了源区成份的不均一性。     

白云鄂博矿床碳酸岩墙/脉和赋矿白云岩中流体包裹体研究

Fluid inclusion study has been carried out for the carbonatite dykes/veins and the ore-hosted dolostone of the Bayan Obo superlarge REE-Fe-Nb deposit in order to provide the evidence and constraint for their origin. Based on the detailed geological observation and mineralogical investigation, the heating and cooling stage and laser Raman spectroscopy were mainly used for the laboratory work of this study. Following results have been obtained： （ 1 ） The discovery of melt and melt-fluid inclusions from carbonatite dykes/veins in the Dulahara and Jianshan Mountains, combined with the fine-grained （aplitic） texture of rocks, as well as the types and features of fluid inclusions such as CO2 enrichment, higher homogenization temperature, provides a direct evidence for the magmatic origin of these dykes/veins. （2） The carbonatite dykes/veins distributed in two regions, nearby the axis of the Kuangou anticline and in the east to Bayan Obo town, mainly show coarse-grained texture. No melt inclusion was found, and the fluid inclusions possess features of less CO2, lower homogenization temperature and higher salinity. They are tentatively identified as veins formed by some carbonate-rich hydrothermal solution. （3） Bedding carbonate layers/lens within the hanging wall and foot wall of ore-hosted dolostone, previously recognized as of magmatic origin, mainly composed by dolomite. The existence of single phase pure aqueous inclusions with very low homogenization temperature indicates their sedimentary origin. （4） The ore-hosted dolostone possesses apparent bedding and laminated structures. No melt inclusion was found, but, both single phase pure aqueous inclusions and CO2 bearing muhi-phase fluid inclusions coexisted in dolostones. In the direction towards ore-bodies, the homogenization temperature and CO2 contents of fluid inclusion show an increasing tendency. It indicates the sedimentary origin of dolostone superimposed by late fluid metasomatism.     

鲁西碳酸岩中磷灰石的原位激光探针分析及其成岩意义

以鲁西雪野和八陡碳酸岩中的磷灰石为对象,运用EMPA和LA-ICP-MS技术,分别测定了它们的主量与微量元素组成,并据此讨论了它们的成岩意义.研究结果表明,这些磷灰石富F(=1.07%～2.74%)贫Cl(＜0.04%),种属为羟氟磷灰石或氟羟磷灰石.微量元素组成上富Sr、Th、U、Pb和轻稀土,是全岩中上述元素的主要载体之一.磷灰石的Sr、F含量与∑REE及LREE/HREE比值均表现出较明显的正相关性,其富Sr、贫Y和富轻稀土等特点与世界典型碳酸岩中的磷灰石相似,但它们具有更高的Sr/Y和Th/U比值,Sr、Ce、Th、Y含量接近地幔中由交代作用形成的磷灰石,说明其寄主碳酸岩岩浆源区应为遭受过流体交代作用的富集地幔.这些磷灰石的(La/Nd)_N比值＞1,(La/Yb)_N比值多数在100以上,与世界其他地区典型碳酸岩中的磷灰石相比铕负异常相对更明显,表明其寄主碳酸岩浆经历一定程度的分异演化.雪野较八陡碳酸岩中磷灰石含更高的F、Sr和∑REE含量及(La/Yb)_N比值,说明其寄主岩浆的演化程度更高.     

碳酸岩研究进展

碳酸岩(carbonatite)一词自首次被提出至今已有一百多年的历史, 它是一种神秘而颇具争议的岩石类型。碳酸岩富含碳酸盐矿物, 通常与基性、超基性或碱性硅酸盐岩伴生形成碳酸岩-硅酸盐岩杂岩体, 具有独特的化学成分和矿物学特征并具有承载重要经济矿床的能力。在过去的几十年里, 碳酸岩的研究在岩石成因及岩浆起源、地球化学与地质年代学、高温高压实验、与碳酸岩相关的经济矿产、碳酸岩型稀土矿床中稀土元素的富集分异及成矿机理等领域取得了巨大进步。本文从碳酸岩的定义与分类、成岩背景与时空分布、岩石学特征及矿物组成、岩浆起源及演化过程以及与碳酸岩相关的矿产资源等方面对碳酸岩的研究进展进行了综述与评论, 提出从成因角度探索碳酸岩分类方案的必要性, 总结和梳理了我国目前发现的碳酸岩的产地和分布特征, 并认为碳酸岩岩浆与硅酸盐岩浆演化具有差异性, 应重视对碳酸岩岩浆演化过程中熔体-流体过渡阶段的研究。最后从文献计量学角度利用大数据和可视化手段对来自Scopus数据库的近十年以"carbonatite"为检索词的近千篇文献进行了可视化分析, 总结归纳了碳酸岩现阶段的研究热点, 并对未来碳酸岩的研究趋势进行了展望。     

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SiO₂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SiO₂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。