Rare earth elements in phoscorites and carbonatites of the Devonian Kola Alkaline Province,Russia: Examples from Kovdor,Khibina, Vuoriyarvi and Turiy Mys complexes

The Devonian (ca. 385–360 Ma) Kola Alkaline Province includes 22 plutonic ultrabasic–alkaline complexes, some of which also contain carbonatites and rarely phoscorites. The latter are composite silicate–oxide–phosphate–carbonate rocks, occurring in close space-time genetic relations with various carbonatites. Several carbonatites types are recognized at Kola, including abundant calcite carbonatites (early- and late-stage), with subordinate amounts of late-stage dolomite carbonatites, and rarely magnesite, siderite and rhodochrosite carbonatites. In phoscorites and early-stage carbonatites the rare earth elements (REE) are distributed among the major minerals including calcite (up to 490 ppm), apatite (up to 4400 ppm in Kovdor and 3.5 wt.% REE₂O₃ in Khibina), and dolomite (up to 77 ppm), as well as accessory pyrochlore (up to 9.1 wt.% REE₂O₃) and zirconolite (up to 17.8 wt.% REE₂O₃). Late-stage carbonatites, at some localities, are strongly enriched in REE (up to 5.2 wt.% REE₂O₃ in Khibina) and the REE are major components in diverse major and minor minerals such as burbankite, carbocernaite, Ca- and Ba-fluocarbonates, ancylite and others. The rare earth minerals form two distinct mineral assemblages: primary (crystallized from a melt or carbohydrothermal fluid) and secondary (formed during metasomatic replacement). Stable (C–O) and radiogenic (Sr–Nd) isotopes data indicate that the REE minerals and their host calcite and/or dolomite have crystallized from a melt derived from the same mantle source and are co-genetic.     

东秦岭地区一种富稀土热液型钡解石的发现及其意义

对东秦岭地区河南嵩县一带进行地质调查,发现了一系列具有一定规模的含稀土碱性碳酸岩矿脉并在其中发现一种特殊的钡解石矿物.依据该钡解石主量元素组成,计算分子式为Ba104Cao81Sral4(CO3)2,为锶钡解石,LA-ICP-MS分析表明其富Na、K、Fe、Mn、Pb、REE、Y等元素,稀土元素总量最高为4 080× ...     

New carbonatite complex in the western Baikal area,southern Siberian craton: Mineralogy,age, geochemistry,and petrogenesis

A dike–vein complex of potassic type of alkalinity recently discovered in the Baikal ledge, western Baikal area, southern Siberian craton, includes calcite and dolomite–ankerite carbonatites, silicate-bearing carbonatite, phlogopite metapicrite, and phoscorite. The most reliable ⁴⁰Ar–³⁹Ar dating of the rocks on magnesioriebeckite from alkaline metasomatite at contact with carbonatite yields a statistically significant plateau age of 1017.4 ± 3.2 Ma. The carbonatite is characterized by elevated SiO₂ concentrations and is rich in K₂O (K₂O/Na₂O ratio is 21 on average for the calcite carbonatite and 2.5 for the dolomite–ankerite carbonatite), TiO₂, P₂O₅ (up to 9 wt %), REE (up to 3300 ppm), Nb (up to 400 ppm), Zr (up to 800 ppm), Fe, Cr, V, Ni, and Co at relatively low Sr concentrations. Both the metapicrite and the carbonatite are hundreds of times or even more enriched in Ta, Nb, K, and LREE relative to the mantle and are tens of times richer in Rb, Ba, Zr, Hf, and Ti. The high (Gd/Yb)_CN ratios of the metapicrite (4.5–11) and carbonatite (4.5–17) testify that their source contained residual garnet, and the high K₂O/Na₂O ratios of the metapicrite (9–15) and carbonatite suggest that the source also contained phlogopite. The Nd isotopic ratios of the carbonatite suggest that the mantle source of the carbonatite was mildly depleted and similar to an average OIB source. The carbonatites of various mineral composition are believed to be formed via the crystallization differentiation of ferrocarbonatite melt, which segregated from ultramafic alkaline melt.     

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。     

Aspects of the geology, petrology and chemistry of some Angolan carbonatites

Using published data and the results of a new study, the main characteristics of seven Angolan carbonatite complexes are here presented. With the exception of the Lupongola complex which intrudes anorthosites, the remaining complexes are hosted by Precambrian silicic rocks. The complexes are of central or dike type and are well exposed. They represent some of the seven morpholithological types present in the province and have some intermediate lithochemical features between those of Brazilian and East African examples.Sovites at Lupongola are the richest in Sr and F, and also have the highest CaO/MgO and La/Y ratios of all sovites studied. Carbonatites from Bonga and Bailundo are the richest in P₂O₅, while those from Coola and Longonjo are the richest in BaO. Ferrocarbonatites from Bailundo and Virulundo have the highest REE contents. TiO₂ contents are usually low. Only Bonga carbonatites show well-defined variation between Ba and Mn contents and the index CaO/(CaO+Fe₂O₃+FeO+MnO+MgO).The CO₂-SiO₂-(Al₂O₃+Na₂O+K₂O) diagram distinguishes silicified carbonatites, feldspar-bearing carbonatites in which the main silicate mineral is K-feldspar, carbonatites and fenites. Potassic fenitization of country rocks is well developed at Bailundo, Bonga and Virulundo, and probably it also affected cogenetic nepheline syenites at Tchivira and Monte Verde.Fluorcarbonates of Ca and REE are encountered in all chemical varieties of carbonatites, and crystallized during late stages of rock formation. They have a strong influence both on total REE contents and on the slopes of chondrite-normalized patterns. Fluorapatite and pyrochlore are other important potential REE host minerals in the rocks studied. The REE patterns usually have discrete negative Ce anomalies, and sometimes show very discrete negative Eu anomalies. Apart from these anomalies, some rocks have very near-linear patterns, but most show inflections, which may occur between light and middle, and between middle and heavy REE. The origins of these variations are still uncertain.Other aspects of rock geochemistry show that, while some features could be explained by crystal fractionation differentiation processes, late-stage or secondary chemical modifications were widespread.     

白云鄂博碳酸岩脉的显微共聚焦激光拉曼光谱分析

白云鄂博矿区发育的脉状稀土碳酸岩，由于其结晶迅速，矿物颗粒细微，其中的微小矿物的鉴定一直是一个难题。应用显微共聚焦激光拉曼光谱仪则能较好地解决这一问题。研究表明，白云鄂博地区存在富稀土白云质岩浆碳酸岩脉，早期阶段形成碱性长石和铁白云石，无稀土矿化；铁白云石常常出溶铁质而自身则形成方解石。霓石和方解石形成略晚，常常与氟碳铈矿等稀土矿物共生，出现强烈的稀土矿化；而无解理的方解石则形成于更晚的岩浆期后热液阶段，发育大量的流体包裹体，并出现强烈的铌、稀土矿化。铌铁矿分布在氟碳铈矿中和赤铁矿边缘，为热液交代作用的产物。早期结晶的矿物如碱性长石、铁白云石稀土矿化弱，岩浆晚期分异出大量的流体相，稀土元素和Sr等进入岩浆热液中，并在热液结晶矿物中富集，甚至在非平衡结晶的石英中产生强烈的稀土矿化。结合岩相学显微观察，显微拉曼探针很好的揭示了这一地质过程。同时为白云鄂博矿床铌、稀土矿化的热液交代成因提供了依据。     

Carbonatite magmatism of the southern Siberian Craton 1 Ga ago: Evidence for the beginning of breakup of Laurasia in the early Neoproterozoic

Apatite and biotite from dolomite?ankerite and calcite?dolomite carbonatite dikes emplaced into the Paleoproterozoic metamorphic rock complex in the southern part of the Siberian Craton are dated by the U–Pb (LA-ICP-MS) and ⁴⁰Ar–³⁹Ar methods, respectively. Proceeding from the lower intercept of discordia with concordia, the age of apatite from calcite?dolomite carbonatite is estimated to be 972 ± 21 Ma and that for apatite from dolomite?ankerite carbonatite, as 929 ± 37 Ma. Values derived from their upper intercept have no geological sense. The ages obtained for biotite by the ⁴⁰Ar–³⁹Ar method are 965 ± 9 and 975 ± 14 Ma. It means that the formation of carbonatites reflects the earliest phases of the Neoproterozoic stage in extension of the continental lithosphere.     

Altered rocks of the Onguren carbonatite complex in the Western Tansbaikal Region: Geochemistry and composition of accessory minerals

The paper discusses the mineralogy and geochemistry of altered rocks associated with calcite and dolomite–ankerite carbonatites of the Onguren dyke–vein complex in the Western Transbaikal Region. The alteration processes in the Early Proterozoic metamorphic complex and synmetamorphic granite hosting carbonatite are areal microclinization and riebeckitization; carbonates, phlogopite, apatite, and aegirine occur in the near-contact zones of the dolomite–ankerite carbonatite veins; and silicification is displayed within separated zones adjacent to the veins. In aluminosilicate rocks, microclinization was accompanied by an increasing content of K, Fe³⁺, Ti, Nb (up to 460 ppm), Th, Cu, and REE; Na, Ti, Fe³⁺, Mg, Nb (up to 1500 ppm), Zr (up to 2800 ppm), Ta, Th, Hf, and REE accumulated in the inner zone of the riebeckitization column. High contents of Ln _Ce (up to 11200 ppm), U (23 ppm), Sr (up to 7000 ppm), Li (up to 400 ppm), Zn (up to 600 ppm), and Th (up to 700 ppm) are typical of apatite–phlogopite–riebeckite altered rock; silicified rock contains up to (ppm): 2000 Th, 20 U, 13000 Ln _Ce, and 5000 Ва. Ilmenite and later rutile are the major Nb carriers in alkali altered rocks. These minerals contain up to 2 and 7 wt % Nb₂O₅, respectively. In addition, ferrocolumbite and aeschynite-(Ce) occur in microcline and riebeckite altered rocks. Fluorapatite containing up to 2.7 wt % (Ln _Ce)₂O₃, monazite-(Ce), cerite-(Ce), ferriallanite-(Ce), and aeschynite-(Ce) are the REE carriers in riebeckite altered rock. Bastnäsite-(Ce), rhabdophane-group minerals, and xenotime-(Y) are typical of silicified rock. Thorite, monazite-(Ce), and rhabdophane-group minerals are the Th carriers.     

Geochronology and mineralogy of the Weishan carbonatite in Shandong province,eastern China

The Weishan REE deposit is located at the eastern part of North China Craton (NCC), western Shandong Province. The REE-bearing carbonatite occur as veins associated with aegirine syenite. LA-ICP-MS bastnaesite Th-Pb ages (129 Ma) of the Weishan carbonatite show that the carbonatite formed contemporary with the aegirine syenite. Based on the petrographic and geochemical characteristics of calcite, the REE-bearing carbonatite mainly consists of Generation-1 igneous calcite (G-1 calcite) with a small amount of Generation-2 hydrothermal calcite (G-2 calcite). Furthermore, the Weishan apatite is characterized by high Sr, LREE and low Y contents, and the carbonatite is rich in Sr, Ba and LREE contents. The δ¹³C_V-PDB (−6.5‰ to −7.9‰) and δ¹³O_V-SMOW (8.48‰–9.67‰) values are similar to those of primary, mantle-derived carbonatites. The above research supports that the carbonatite of the Weishan REE deposit is igneous carbonatite. Besides, the high Sr/Y, Th/U, Sr and Ba of the apatite indicate that the magma source of the Weishan REE deposit was enriched lithospheric mantle, which have suffered the fluid metasomatism. Taken together with the Mesozoic tectono-magmatic activities, the NW and NWW subduction of Izanagi plate along with lithosphere delamination and thinning of the North China plate support the formation of the Weishan REE deposit. Accordingly, the mineralization model of the Weishan REE deposit was concluded: The spatial-temporal relationships coupled with rare and trace element characteristics for both carbonatite and syenite suggest that the carbonatite melt was separated from the CO₂-rich silicate melt by liquid immiscibility. The G-1 calcites were crystallized from the carbonatite melt, which made the residual melt rich in rare earth elements. Due to the common origin of G-1 and G-2 calcites, the REE-rich magmatic hydrothermal was subsequently separated from the melt. After that, large numbers of rare earth minerals were produced from the magmatic hydrothermal stage.     

Fluid–rock reactions in the 1.3 Ga siderite carbonatite of the Grønnedal–Íka alkaline complex,Southwest Greenland

Petrogenetic studies of carbonatites are challenging, because carbonatite mineral assemblages and mineral chemistry typically reflect both variable pressure–temperature conditions during crystallization and fluid–rock interaction caused by magmatic–hydrothermal fluids. However, this complexity results in recognizable alteration textures and trace-element signatures in the mineral archive that can be used to reconstruct the magmatic evolution and fluid–rock interaction history of carbonatites. We present new LA–ICP–MS trace-element data for magnetite, calcite, siderite, and ankerite–dolomite–kutnohorite from the iron-rich carbonatites of the 1.3 Ga Grønnedal–Íka alkaline complex, Southwest Greenland. We use these data, in combination with detailed cathodoluminescence imaging, to identify magmatic and secondary geochemical fingerprints preserved in these minerals. The chemical and textural gradients show that a 55 m-thick basaltic dike that crosscuts the carbonatite intrusion has acted as the pathway for hydrothermal fluids enriched in F and CO₂, which have caused mobilization of the LREEs, Nb, Ta, Ba, Sr, Mn, and P. These fluids reacted with and altered the composition of the surrounding carbonatites up to a distance of 40 m from the dike contact and caused formation of magnetite through oxidation of siderite. Our results can be used for discrimination between primary magmatic minerals and later alteration-related assemblages in carbonatites in general, which can lead to a better understanding of how these rare rocks are formed. Our data provide evidence that siderite-bearing ferrocarbonatites can form during late stages of calciocarbonatitic magma evolution.     

Uranium and thorium in carbonatitic minerals from the Guli massif, Polar Siberia

This paper reports a geochemical and mineralogical study on carbonatites from the Guli massif, which hosts rare-metal mineralization. The principal carriers of radioactive elements in the carbonatites are pyrochlore-group minerals, zirconolite, and thorianite, which are described here. They are characterized by elevated concentrations (wt %) of radioactive elements: up to 17.89 UO₂ and 20.01 ThO₂ in pyrochlore, up to 6.49 UO₂ and 94.29 ThO₂ in thorianite, and up to 6.74 ThO₂ in zirconolite. The pyrochlore-group minerals, zirconolite, and thorianite from the early calcite carbonatites occur in intimate association with Ti-Zr oxides calzirtite, perovskite, and baddeleyite. Significant radioactive element fractionation in early-stage derivatives results in the depletion of the residual magmatic products in these elements. The dolomite carbonatites are reported to contain only trace amounts of pyrochlore-group minerals. It was shown that the distribution of U, Th, Nb, and Ta in the calcite and dolomite carbonatites is correlated with the evolutionary trends of pyrochlore composition. Typical schemes of isomorphic substitution are proposed for pyrochlore-group minerals and zirconolite. The pyrochlore-group minerals show an apparent evolutionary trend from U-rich towards more Th- and Ta-rich varieties, and Ba-Sr cation-deficient varieties originate during the latest stage of the evolution. The pyrochlore-group minerals, zirconolite, and thorianite may also accumulate in placers, together with gold. Because of the relative ease of extraction of the accessory minerals, the carbonatites of the Guli massif can be considered as commercial sources of radioactive raw materials.     

Pb/Pb age determinations on the Newania and Sevattur carbonatites of India: evidence for multi-stage histories

The ages of Indian carbonatites are still controversial. Most of the earlier datings were done by K/Ar methods. We therefore analysed Pb/Pb ratios in carbonatites from carbonatite-alkalic complexes of Newania (NW India, Rajasthan State) and Sevattur (SW India, Tamil Nadu State) to constrain the age and geological history of these rocks. Newania carbonatites are intrusive into Precambrian Untala granite-gneiss and mainly dolomitic in composition (rauhaugite) followed by a later phase of ankerite carbonatite, while thin calcite carbonatite (sövite) dykelets are the youngest in the sequence. The analysed whole-rock samples are characterised by ²⁰⁶Pb/²⁰⁴Pb ratios between 60 and 176 and ²⁰⁷Pb/²⁰⁴Pb ratios between 22 and 40, which are extremely high in comparison to common igneous rocks and even for carbonatite compositions. One sample, New 37, shows the extreme ratios of ²⁰⁶Pb/²⁰⁴Pb = 574 and ²⁰⁷Pb/²⁰⁴Pb = 73. This requires a μ-value of about 2000 for the last 1550 Ma. If the samples are classified according to their petrographic/geochemical characteristics this results in an isochron age of 1551 ± 46 Ma for the ankerite carbonatites (six samples). The dolomites (6 samples) yield an isochron age of 2.27 Ga. Although these results fit quite well into the geological evolution scheme of the area, the extreme long age hiatus between dolomite carbonatite and ferrocarbonatite formation events raises severe problems for their petrologic interpretation.

The Proterozoic Sevattur carbonatite complex (SCC, Tamil Nadu) was emplaced contemporaneously with a large number of carbonatite complexes within the Precambrian gneissic terrane of the Eastern Ghats Mobile Belt. The main mass is composed of dolomite carbonatite (rauhaugite) with a few dikes of calcite carbonatite (sövite) and ankerite carbonatite within it. All eight samples together yield an isochron of 805 ± 10 Ma. This isochron is mainly determined on ankerite carbonatites with μ-values up to 1900 for the last 800 Ma. Taking only ankerite carbonatites into account, the resulting age is 801 ± 11 Ma. The ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios of these samples are similar to the main group of Newania and far beyond the isotopic composition of common igneous rocks.

Our investigations show that in carbonatitic rock systems extremely high lead isotopic ratios can be established due to the crystallization of uranium-rich mineral phases. In both cases the observed high to extremely high initial Pb isotope ratios require the residence of the lead in intermediate high-μ reservoirs either within the upper mantle or the crust prior to the carbonatite formation. A high-temperature event, which completely reset the Rb/Sr and K/Ar isotopic systems of Nevania carbonatites, seems to have no influence on the lead isotopic systematics.     

Postorogenic carbonatites at Eden Lake, Trans-Hudson Orogen (northern Manitoba, Canada): Geological setting, mineralogy and geochemistry

The Eden Lake pluton in the Trans-Hudson Orogen is the first known occurrence of carbonatites in Manitoba. The pluton is largely made up of modally and geochemically diverse syenitic rocks derived from postorogenic magma(s) of shoshonitic affinity. Their diversity can be accounted for by a combination of crystal fractionation and fluid release in the final evolutionary stage (crystallization of quartz alkali-feldspar syenite). At Eden Lake, carbonatites, represented predominantly by coarse-grained massive to foliated sövite, occur as branching veins and lenticular bodies up to 4 m in thickness showing crosscutting relations with respect to all of the syenitic units. The host rocks are intensely fenitized at the contact, and there is also abundant mineralogical and textural evidence for assimilation of silicate material by carbonatitic magma through wallrock reaction and xenolith fragmentation and digestion. The bulk of the carbonatites are composed of (in order of crystallization): Sr–REE-rich fluorapatite, aegirine–augite, and coarse calcite crystals surrounded by fine-grained calcite (on average,  90 vol.% of the rock). Noteworthy accessory constituents are celestine, bastnäsite-(Ce) (both as primary inclusions in calcite), Nb–Zr–rich titanite, low-Hf zircon, allanite-(Ce) and andradite. The calcite is chemically uniform (Sr-rich, Mg–Mn–Fe-poor and low in ¹³C), but shows clear evidence of ductile deformation and syndeformational cataclasis. Geochemically, the carbonatites are enriched in Sr, Ba, light rare-earth elements, Th and U, but depleted in high-field-strength elements (particularly, Ti, Nb and Ta). The stable-isotope composition of coarse- and fine-grained calcite from the carbonatites and interstitial calcite from syenites is remarkably uniform: ca. − 8.16 ± 0.27‰ δ¹³C (PDB) and + 8.04 ± 0.19‰ δ¹⁸O (SMOW). The available textural and geochemical evidence indicates that the Eden Lake carbonatites are not consanguineous with the associated syenites and may have been derived from a Nb–Ti-retentive and ¹³C-depleted source such as the subducted crustal material underlying the Eden Lake deformation corridor.     

The mineralogy of copper-bearing skarn to the east of the Sungun-Chay river, East-Azarbaidjan, Iran

A calcic copper-bearing skarn zone in East-Azarbaidjan, NW of Iran is located to the east of the Sungun-Chay river. Skarn-type metasomatic alteration and mineralization occurs along the contact between Upper Cretaceous impure carbonates and an Oligo-Miocene Cu-bearing granitoid stock. Both endoskarn and exoskarn are developed along the contact. Exoskarn is the principal skarn zone enclosed by a marmorized and skarnoid–hornfelsic zone. The skarnification process occurred two stages: (1) prograde and (2) retrograde. The prograde stage is temporally and spatially divided into two sub-stages: (a) metamorphic–bimetasomatic (sub-stage I) and (b) prograde metasomatic (sub-stage II). Sub-stage I began immediately after the intrusion of the pluton into the enclosing impure carbonates. Sub-stage II commenced with segregation and evolution of a fluid phase in the pluton and its invasion into fractures and micro-fractures of the marmorized and skarnoid–hornfelsic rocks developed during sub-stage I. The introduction of considerable amounts of Fe, Si and Mg led to the development of substantial amounts of medium- to coarse-grained anhydrous calc-silicates. From texture and mineralogy the retrograde metasomatic stage can be divided into two discrete sub-stages: (a) early (sub-stage III) and (b) late (sub-stage IV). During sub-stage III, the previously formed skarn zones were affected by intense multiple hydro-fracturing phases in the Cu-bearing stock. In addition to Fe, Si and Mg, substantial amounts of Cu, Pb, Zn, along with volatile components such as H₂S and CO₂ were added to the skarn system. Consequently considerable amounts of hydrous calc-silicates (epidote, tremolite–actinolite), sulfides (pyrite, chalcopyrite, galena, sphalerite, bornite), oxides (magnetite, hematite) and carbonates (calcite, ankerite) replaced the anhydrous calc-silicates. Sub-stage IV was concurrent with the incursion of relatively low temperature, more highly oxidizing fluids into skarn system, bringing about partial alteration of the early-formed calc-silicates and developing a series of very fine-grained aggregates of chlorite, clay, hematite and calcite.     

Unusual rocks and mineralisation in a new carbonatite complex at Kandaguba, Kola Peninsula, Russia

The paper presents the results from a reconnaissance investigation of carbonatites in a newly discovered alkaline complex in the Kola peninsula, Russia. The Kandaguba complex differs from other carbonatite plutons of the Kola alkaline province by (a) the absence of ultrabasic rocks, (b) widespread occurrence of nepheline-, cancrinite- and nepheline–cancrinite syenites and carbonatites and (c) presence of apatite–calcite ijolites and feldspar ijolites as separate intrusive phase. The Kandaguba carbonatites are notable for the predominance of late ferromagnesian varieties together with quartz and numerous accessory mineral species. The association of phosphates (monazite, gorseixite, goyazite, apatite), sulphides and tellurides (pyrite, sphalerite, galena, hessite), ilmenorutile, barite with quartz and ankerite is a remarkable feature of these carbonatites. The Kandaguba carbonatites are inferred to have been generated as the products of liquid immiscibility followed by differentiation of the carbonatite melt.     

Cymrite as an indicator of high barium activity in the formation of hydrothermal rocks related to carbonatites of the Kola Peninsula

Cymrite, BaAl₂Si₂O₈ · nH₂O, is a rare mineral formed during low-grade dynamothermal metamorphism (T = 250–300°C, P = 1–3 kbar). Cymrite has been described from many metasedimentary ores and hydrothermal rocks. In carbonatites, it has been found for the first time. Cymrite has been identified in the Kovdor and Seblyavr massifs, Kola Peninsula. In Kovdor, this mineral has been described from one of the hydrothermal veins cutting the pyroxenite-melilitite-ijolite complex at the Phlogopite deposit; cymrite is associated with thomsonite, calcite, and stivensite. In the Seblyavr pluton, cymrite occurs in thin veins of calcite carbonatite that cut pyroxenite contacting with ijolite. Cymrite from the Seblyavr pluton is associated with calcite, natrolite, pyrite, and chalcopyrite. The mineral is optically negative and uniaxial, with extinction parallel to elongation; ω ～ 1.607(1). According to X-ray diffraction data, cymrite from Seblyavr is monoclinic, space group P1m1; unit-cell dimensions are: a = 5.33, b = 36.96, c = 7.66 Å, β = 90°, V = 1510.55 ų. According to the results of IR spectroscopy, in the series of samples from different massifs (in the running order Kovdor-Voishor-Seblyavr), the double-layer deformation is enhanced and accompanied by a decrease in the Si-O-Si angle and weakening of hydrogen bonds of interlayer water. The empirical formulas of cymrite calculated from electron microprobe analyses are Ba_0.93–0.95Ca_0.01–0.02K_0.00–0.05Na_0.02–0.04Al_1.97–2.01Si_1.99–2.03O₈(H₂O) and Ba_1.00–1.02Ca_0.00–0.01Sr_0.00–0.01Fe_0.00–0.01Al_1.94–2.00Si_1.98–2.03O₈(H₂O) at Seblyavr and Kovdor, respectively. Cymrite from the carbonatite massifs of the Kola Peninsula was formed under hydrothermal conditions at low temperature (200–300°C), high activity of Ba and Si, and high water pressure. At Kovdor, the mineral crystallized directly from the residual solution enriched in Ba. The sequence of mineral deposition is as follows: thomsonite-cymrite-calcite-stevensite. Cymrite from the Seblyavr pluton is a product of hydrothermal alteration of primary Na-K-Ba silicates of ijolite: nepheline, feldspar, and probably celsian. Natrolite replaces cymrite indicating high alkalinity of late hydrothermal fluids.     

华北北缘东段开原地区三叠纪侵入岩年代学及岩石地球化学研究

本文报道了位于华北北缘东段开原地区尖山子岩体、宝兴岩体和树德屯岩体的岩相学、岩石地球化学及年代学特征,探讨了上述岩体的形成时代、岩石成因及其构造环境。锆石U-Pb定年结果表明,尖山子岩体形成于251±1.3Ma,宝兴岩体形成于235±1.3Ma,树德屯岩体形成于224±1.9Ma,说明开原地区三叠纪存在早三叠世、中三叠世和晚三叠世三个时期的岩浆活动。尖山子岩体以二长花岗岩为主,具高硅低镁特征,属钙碱性系列;富集大离子亲石元素Rb、K、Ba、Th,相对亏损Ta、Nb、P、Hf、Zr等高强场元素;δEu=0.55~1.87,(La/Yb)N=6.23~47.9,轻重稀土分馏明显,富集轻稀土,亏损重稀土。宝兴岩体以花岗闪长岩为主,Si O2含量变化较大(52.36%~74.06%),Al2O3含量(14.5%~17.34%),Mg O含量(0.61%~3.66%),属钙碱性系列;富集大离子亲石元素Rb、K、Ba、Th,相对亏损Ta、Nb、P、Ti等高强场元素;无明显的Eu异常,(La/Yb)N=6.81~25.6,轻重稀土分馏较明显,富集轻稀土,亏损重稀土。树德屯岩体以闪长岩为主,岩石具有低硅高镁特征,K2O/Na2O比值为0.33~0.76,显示富K贫Na特征,属钙碱性系列;富集大离子亲石元素Rb、K、Ba、Th,相对亏损Ta、Nb、P、Ti、Hf、Zr等高强场元素;无明显的Eu异常,(La/Yb)N=3.87~10.2,轻重稀土分馏不明显。上述岩石地球化学特征表明,尖山子岩体和宝兴岩体的原始岩浆起源于下地壳基性物质的部分熔融,树德屯岩体的原始岩浆起源于亏损的地幔楔。研究区三叠纪岩浆岩形成于造山阶段挤压环境下。华北北缘东段的挤压碰撞作用一直持续到晚三叠世(224Ma),而造山阶段向造山后阶段的构造转换(挤压地壳加厚向伸展垮塌的环境转换)发生于晚三叠世-早侏罗世(224~180Ma)期间。华北北缘东段中生代岩石圈减薄或破坏始于晚三叠世-早侏罗世(224~180Ma)期间。     

Compositions of magmas,formation conditions,and genesis of carbonate-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex,eastern Sayan

Based on the investigation of melt inclusions using electron and ion microprobe analysis, we estimated the composition, evolution, and formation conditions of magmas responsible for the calcite-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex (eastern Sayan, Russia). Primary melt and coexisting crystalline inclusions were found in the nepheline and calcite of these rocks. Diopside, amphibole (?), perovskite, potassium feldspar, apatite, calcite, pyrrhotite, and titanomagnetite were identified among the crystalline inclusions. The melt inclusions in nepheline from the ijolites are completely crystallized. The crystalline daughter phases of these inclusions are diopside, phlogopite, apatite, calcite, magnetite, and cuspidine. During thermometric experiments with melt inclusions in nepheline, the complete homogenization of the inclusions was attained through the dissolution of a gas bubble at temperatures of 1120–1130°C. The chemical analysis of glasses from the homogenized melt inclusions in nepheline of the ijolites revealed significant variations in the content of components: from 36 to 48 wt % SiO₂, from 9 to 21 wt % Al₂O₃, from 8 to 25 wt % CaO, and from 0.6 to 7 wt % MgO. All the melts show very high contents of alkalis, especially sodium. According to the results of ion microprobe analysis, the average content of water in the melts is no higher than a few tenths of a percent. The most salient feature of the melt inclusions is the extremely high content of Nb and Zr. The glasses of melt inclusions are also enriched in Ta, Th, and light rare earth elements but depleted in Ti and Hf. Primary melt inclusions in calcite from the carbonatites contain a colorless glass and daughter phlogopite, garnet, and diopside. The silicate glass from the melt inclusions in calcite of the carbonatite is chemically similar to the glasses of homogenized melt inclusions in nepheline from the ijolites. An important feature of melt inclusions in calcite of the carbonatites is the presence in the glass of carbonate globules corresponding to calcite in composition. The investigation of melt inclusions in minerals of the ijolites and carbonatites and the analysis of the alkaline and ore-bearing rocks of the Belaya Zima Massif provided evidence for the contribution of crystallization differentiation and silicate-carbonate liquid immiscibility to the formation of these rocks. Using the obtained trace-element compositions of glasses of homogenized melt inclusions and various alkaline rocks and carbonatites, we determined to a first approximation the compositions of mantle sources responsible for the formation of the rock association of the Belaya Zima alkaline-carbonatite complex. The alkaline rocks and carbonatites were derived from the depleted mantle affected by extensive metasomatism. It is supposed that carbonate melts enriched in sodium and calcium were the main agents of mantle metasomatism.     

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.     

S, C, O, H Isotope Data and Noble Gas Studies of the Maoniuping LREE Deposit, Sichuan Province, China： A Mantle Connection for Mineralization

The Maoniuping REE deposit, located about 22 km to the southwest of Mianning, Sichuan Province, is the second largest light REE deposit in China, subsequent to the Bayan Obo Fe-Nb-REE deposit in the Inner Mongolia Autonomous Region. Tectonically, it is located in the transitional zone between the Panxi rift and the Longmenshan-Jinpingshan orogenic zone. It is a carbonatite vein-type deposit hosted in alkaline complex rocks. The bastnaesite-barite, bastnaesite-calcite, and bastnaesite-microcline lodes are the main three types of REE ore lodes. Among these, the first lode is distributed most extensively and its REE mineralization is the strongest. Theδ34Sv-CDT values of the barites in the ore of the deposit vary in a narrow range of +5.0 to +5.1‰in the bastnaesite-calcite lode and +3.3 to +5.9‰in the bastnaesite-barite lode, showing the isotopic characteristics of magma-derived sulfur. Theδ13Cv-PDB values and theδ518OV-SMOW values in the bastnaesite-calcite lode range from -3.9 to -6.9‰and from +7.3 to +9.7‰, respectively, which fall into the range of "primary carbonatites", showing that carbon and oxygen in the ores of the Maoniuping deposit were derived mainly from a deep source. Theδ13Cv-PDB values of fluid inclusions vary from -3.0 to -5.6‰, with -3.0 to -4.0‰in the bastnaesite-calcite lode and -3.0 to -5.6‰in the bastnaesite-barite lode, which show characteristics of mantle-derived carbon. TheδDv-SMOW values of fluid inclusions range from -57 to -88‰, with -63 to -86‰in the bastnaesite-calcite lode and -57 to -88‰in the bastnaesite-barite lode, which show characteristics of mantle-derived hydrogen. Theδ18OH2OV-SMOW values vary from +7.4 to +8.6‰in the bastnaesite calcite lode, and +6.7 to +7.8‰in the bastnaesite-barite lode, almost overlapping the range of +5.5 to +9.5‰for magmatic water. The 4He content, R/Ra ratios are (13.95 to 119.58×10-6 (cm3/g)STP and 0.02 to 0.11, respectively, and 40Ar/36Ar is 313±1 to 437±2. Considering the 4He increase caused by high contents of radioactive elements, a mantle-derived fluid probably exists in the inclusions in the fluorite, calcite and bastnaesite samples. The Maoniuping deposit and its associated carbonatite-alkaline complex were formed in 40.3 to 12.2 Ma according to K-Ar and U-Pb data. All these data suggest that large quantities of mantle fluids were involved in the metallogenic process of the Maoniuping REE deposit through a fault system.