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.     

Trace-element composition and zoning in clinopyroxene- and amphibole-group minerals: Implications for element partitioning and evolution of carbonatites

The present work is a first comprehensive study of the trace-element composition and zoning in clinopyroxene- and amphibole-group minerals from carbonatites, incorporating samples from 14 localities worldwide (Afrikanda, Aley, Alnö, Blue River, Eden Lake, Huayangchuan, Murun, Oka, Ozernaya Varaka, Ozernyi, Paint Lake, Pinghe, Prairie Lake, Turiy Mys). The new electron-microprobe data presented here significantly extend the known compositional range of clinopyroxenes and amphiboles from carbonatites. These data confirm that calcic and sodic clinopyroxenes from carbonatites are not separated by a compositional gap, instead forming an arcuate trend from nearly pure diopside through intermediate aegirine–augite compositions confined to a limited range of CaFeSi₂O₆ contents (15–45 mol%) to aegirine with < 25 mol% of CaMgSi₂O₆ and a negligible proportion of CaFeSi₂O₆. A large set of LA-ICPMS data shows that the clinopyroxenes of different composition are characterized by relatively low levels of Cr, Co and Ni (≤ 40 ppm) and manifold variations in the concentration of trivalent lithophile and some incompatible elements (1–150 ppm Sc, 26–6870 ppm V, 5–550 ppm Sr, 90–2360 ppm Zr, and nil to 150 ppm REE), recorded in some cases within a single crystal. The relative contribution of clinopyroxenes to the whole-rock Rb, Nb, Ta, Th and U budget is negligible. The major-element compositional range of amphiboles spans from alkali- and Al-poor members (tremolite) to Na–Al-rich Mg- or, less commonly, Fe-dominant members (magnesiohastingsite, hastingsite and pargasite), to calcic–sodic, sodic and potassic–sodic compositions intermediate between magnesio-ferrikatophorite, richterite, magnesioriebeckite, ferri-nyböite and (potassic-)magnesio-arfvedsonite. In comparison with the clinopyroxenes, the amphiboles contain similar levels of tetravalent high-field-strength elements (Ti, Zr and Hf) and compatible transition elements (Cr, Co and Ni), but are capable of incorporating much higher concentrations of Sc and incompatible elements (up to 500 ppm Sc, 43 ppm Rb, 1470 ppm Sr, 1230 ppm Ba, 80 ppm Pb, 1070 ppm REE, 140 ppm Y, and 180 ppm Nb). In some carbonatites, amphiboles contribute as much as 25% of the Zr + Hf, 15% of the Sr and 35% of the Rb + Ba whole-rock budget. Both clinopyroxenes and amphiboles may also host a significant share (~ 10%) of the bulk heavy-REE content. Our trace-element data show that the partitioning of REE between clinopyroxene (and, in some samples, amphibole) and the melt is clearly bimodal and requires a revision of the existing models assuming single-site REE partitioning. Clinopyroxenes and amphiboles from carbonatites exhibit a diversity of zoning patterns that cannot be explained exclusively on the basis of crystal chemistry and relative compatibility of different trace-element in these minerals. Paragenetic analysis indicates that in most cases, the observed zoning patterns develop in response to removal of selected trace elements by phases co-precipitating with clinopyroxene and amphibole (especially magnetite, fluorapatite, phlogopite and pyrochlore). With the exception of magnesiohastingsite–richterite sample from Afrikanda, the invariability of trace-element ratios in the majority of zoned clinopyroxene and amphibole crystals implies that fluids are not involved in the development of zoning in these minerals. The implications of the new trace-element data for mineral exploration targeting REE, Nb and other types of carbonatite-hosted rare-metal mineralization are discussed.     

Genesis of Si-rich carbonatites in Huanglongpu Mo deposit,Lesser Qinling orogen,China and significance for Mo mineralization

The Huanglongpu carbonatite-related Mo ore field is located in the Lesser Qinling Orogenic belt in the southern margin of the North China block. The ore field is composed of six deposits, Yuantou, Wengongling, Dashigou, Shijiawan, Taoyuan and Erdaohe, all of which are genetically related to carbonatite dykes except for the Shijiawan deposit which is associated with a granitic porphyry. The Yuantou carbonatite dykes intruded into Archean gneiss and other carbonatites emplaced into Mesoproterozoic volcanic and sediment rocks. The carbonatites are mainly composed of calcite and variable amounts of quartz and K-feldspar and minor molybdenite. Re–Os dating of molybdenite from the Yuantou carbonatite yields a weighted average age of 225.0 ± 7.6 Ma, consistent with the molybdenite age (221 Ma) from the Dashigou deposit. The rocks are characterized by high heavy REE (HREE) contents and consistent flat REE distribution patterns with La/Yb_cn ~ 1. Quartz in the carbonatites from Yuantou and Dashigou deposits shows consistent O isotopes (8.1–10.2‰) similar to the associated calcite (7.2–9.5‰). The quartz and associated K-feldspar contain lower Zr, Hf and higher HREE abundances and negligible Eu anomaly relative to those from the granite porphyry in Shijiawan. Both minerals are primary products in the carbonatitic liquid, and not captured from the wall-rocks or crustal-derived silicate magmas, or a hydrothermal origin. Thus, the Huanglongpu carbonatitic liquids were enriched in Si and Mo, which may be produced by intensely fractional crystallization of non-silicate minerals.     

Carbonatite-hosted niobium deposit at Aley,northern British Columbia (Canada): Mineralogy,geochemistry and petrogenesis

The Aley Nb deposit in northern British Columbia, Canada, is hosted by metamorphosed calcite and dolomite carbonatites of anorogenic affinity emplaced in Lower Paleozoic sedimentary carbonate rocks in the Devonian. Primary Nb mineralization consists of pyrochlore (commonly comprising a U–Ta-rich and F-poor core) and ferrocolumbite developed as discrete crystals and replacement products after the pyrochlore. These phases and associated heavy minerals (apatite ± magnetite ± zircon ± baddeleyite) precipitated early in the magmatic history and probably formed laterally extensive cumulate layers up to at least 1.5 m in thickness. Fractionation of copious amounts of pyrochlore is reflected in the chemical composition of the carbonatites and their constituent minerals, which show large variations in Nb/Ta value, but a near-chondritic Zr/Hf ratio. Alkali-rich metasomatic rocks (in particular, fenites and glimmerites) associated with the carbonatites are barren; the bulk of Nb in these rocks is contained in rutile, phlogopite and, to a much lesser extent, amphibole. When the passive margin of North America became the zone of plate convergence in the Cretaceous, the host carbonatites were strongly deformed, which is manifested in structures and textures indicative of grain comminution, ductile flow, folding and, locally, brecciation. The structure and continuity of the cumulate units enriched in Nb minerals were profoundly affected by these processes. Interaction of the carbonatites with crustal fluids of complex chemistry resulted in extensive dolomitization, replacement of the pyrochlore and ferrocolumbite by fersmite, and development of hydrothermal parageneses consistent with the lower greenschist-facies conditions. At these late evolutionary stages, Nb was mobilized only to a very limited extent and sequestered in a variety of minerals (fersmite, euxenite, Mg-rich ferrocolumbite and Nb-bearing rutile) typically occurring as scarce minute crystals associated with hydrothermal dolomite, quartz and chlorite. Progressive enrichment of the deformed dolomite carbonatites in heavy C and O isotopes relative to primary calcite, coupled with changes in the trace-element composition of Nb phases, indicate that the fluids were equilibrated with the wall-rock sedimentary rocks hosting the Aley deposit and were capable of transporting F⁻, (PO₄)^3 −, U, Th and rare-earth elements, but not Nb.     

Petrological and geochemical characteristics of Zhaibei granites in Nanling region,Southeast China: Implications for REE mineralization

Mineralization with ion adsorption rare earth elements (REEs) in the weathering profile of granitoid rocks from Nanling region of Southeast China is an important REE resource, especially for heavy REE (HREE) and Y. However, the Jurassic granites in Zhaibei which host the ion adsorption light REE (LREE) ores are rare. It is of peraluminous and high K calc-alkaline composition, which has similar geochemical features of high K₂O + Na₂O and Zr + Nb + Ce + Y contents and Ga/Al ratio to A-type granite. Based on the chemical discrimination criteria of Eby [Geology 20 (1992) 641], the Zhaibei granite belongs to A1-type and has similar source to ocean island basalts. The rock is enriched in LREE and contains abundant REE minerals including LREE-phosphates and halides. Minor LREE was also determined in the feldspar and biotite, which shows negligible and negative Eu anomalies, respectively. This indicates that the Zhaibei granite was generated by extreme differentiation of basaltic parent magmas. In contrast, granites associated with ion adsorption HREE ores contain amounts of HREE minerals, and show similar geochemical characteristics with fractionated felsic granites. Note that most Jurassic granitoids in the Nanling region contain no REE minerals and cannot produce REE mineralization. They belong to unfractionated M-, I- and S-type granites. Therefore, accumulation of REE in the weathering profile is controlled by primary REE mineral compositions in the granitoids. Intense fractional crystallization plays a role on REE enrichment in the Nanling granitoid rocks.     

REE mineralogy and geochemistry of the Western Keivy peralkaline granite massif,Kola Peninsula,Russia

The authors have studied the geology, geochemistry, petrology and mineralogy of the rare earth elements (REE) occurring in the Western Keivy peralkaline granite massif (Kola Peninsula, NW Russia) aged 2674 ± 6 Ma. The massif hosts Zr- and REE-rich areas with economic potential (e.g. the Yumperuaiv and Large Pedestal Zr-REE deposits), where 25% of ΣREE are represented by heavy REE (HREE). The main REE minerals are: chevkinite-(Ce), britholite-(Y) and products of their metamict decay, bastnäsite-(Ce), allanite-(Ce), fergusonite-(Y), monazite-(Ce), and others. The areas contain also significant quantities of zircon reaching potentially economic levels. We have discovered that behavior of REE and Zr is controlled by alkalinity of melt/solution, which, in turn, is controlled by crystallization of alkaline pyroxenes (predominantly aegirine) and amphiboles (predominantly arfvedsonite) at a late magmatic stage. Crystallization of mafic minerals leads to a sharp increase of K₂O content and decrease of SiO₂ content that cause a decrease of melt viscosity and REE and Zr solubility in the liquid. Therefore, REE and zirconium immediately precipitate as zircon and REE-minerals. There are numerous pod- and lens-like granitic pegmatites within the massif. Pegmatites in the REE-rich areas are also enriched in REE, but HREE prevails over light REE (LREE), about 88% of REE sum.     

Mineralogy,geochemistry and the origin of high-phosphorus oolitic iron ores of Aswan,Egypt

The Coniacian-Santonian high-phosphorus oolitic iron ore at Aswan area is one of the major iron ore deposits in Egypt. However, there are no reports on its geochemistry, which includes trace and rare earth elements evaluation. Texture, mineralogy and origin of phosphorus that represents the main impurity in these ore deposits have not been discussed in previous studies. In this investigation, iron ores from three localities were subjected to petrographic, mineralogical and geochemical analyses. The Aswan oolitic iron ores consist of uniform size ooids with snowball-like texture and tangentially arranged laminae of hematite and chamosite. The ores also possess detrital quartz, apatite and fine-grained ferruginous chamosite groundmass. In addition to Fe₂O₃, the studied iron ores show relatively high contents of SiO₂ and Al₂O₃ due to the abundance of quartz and chamosite. P₂O₅ ranges from 0.3 to 3.4 wt.% showing strong positive correlation with CaO and suggesting the occurrence of P mainly as apatite. X-ray diffraction analysis confirmed the occurrence of this apatite as hydroxyapatite. Under the optical microscope and scanning electron microscope, hydroxyapatite occurred as massive and structureless grains of undefined outlines and variable size (5–150 μm) inside the ooids and/or in the ferruginous groundmass. Among trace elements, V, Ba, Sr, Co, Zr, Y, Ni, Zn, and Cu occurred in relatively high concentrations (62–240 ppm) in comparison to other trace elements. Most of these trace elements exhibit positive correlations with SiO₂, Al₂O₃, and TiO₂ suggesting their occurrence in the detrital fraction which includes the clay minerals. ΣREE ranges between 129.5 and 617 ppm with strong positive correlations with P₂O₅ indicating the occurrence of REE in the apatite. Chondrite-normalized REE patterns showed LREE enrichment over HREE ((La/Yb)_N = 2.3–5.4) and negative Eu anomalies (Eu/Eu* = 0.75–0.89). The oolitic texture of the studied ores forms as direct precipitation of iron-rich minerals from sea water in open space near the sediment-water interface by accretion of FeO, SiO_2, and Al₂O₃ around suspended solid particles such as quartz and parts of broken ooliths. The fairly uniform size of the ooids reflects sorting due to the current action. The geochemistry of major and trace elements in the ores reflects their hydrogenous origin. The oolitic iron ores of the Timsha Formation represent a transgressive phase of the Tethys into southern Egypt during the Coniacian-Santonian between the non-marine Turonian Abu Agag and Santonian-Campanian Um Barmil formations. The abundance of detrital quartz, positive correlations between trace elements and TiO₂ and Al₂O₃, and the abundance mudstone intervals within the iron ores supports the detrital source of Fe. This prediction is due to the weathering of adjacent land masses from Cambrian to late Cretaceous. The texture of the apatite and the REE patterns, which occurs entirely in the apatite, exhibits a pattern similar to those in the granite, thus suggesting a detrital origin of the hydroxyapatite that was probably derived from the Precambrian igneous rocks. Determining the mode of occurrence and grain size of hydroxyapatite assists in the maximum utilization of both physical and biological separation of apatite from the Aswan iron ores, and hence encourages the use of these ores as raw materials in the iron making industry.     

The composition and genesis of the Mesoarchean Dagushan banded iron formation (BIF) in the Anshan area of the North China Craton

The Dagushan BIF-hosted iron deposit in the Anshan–Benxi area of the North China Craton (NCC) has two types of iron ore: quartz–magnetite BIF (Fe₂O₃^T < 57 wt.%) and high-grade iron ore (Fe₂O₃^T > 90 wt.%). Chlorite-quartz schist and amphogneiss border the iron orebodies and are locally present as interlayers with BIFs; chlorite-quartz schist and BIFs are enclosed by amphogneiss in some locations. The quartz–magnetite BIFs are enriched in HREEs (heavy rare earth elements) with positive La, Eu and Y anomalies, indicating their precipitation from marine seawater with a high-temperature hydrothermal component. Moreover, these BIFs have low concentrations of Al₂O₃, TiO₂ and HFSEs (high field strength elements, e.g., Zr, Hf and Ta), suggesting that terrigenous detrital materials contributed insignificantly to the chemical precipitation. The high-grade iron ores exhibit similar geochemical signatures to the quartz–magnetite BIFs (e.g., REE patterns and Y/Ho ratios), implying that they have identical sources of iron. However, these ores have different REE (rare earth element) contents and Eu/Eu* values, and the magnetites contained within them exhibit diverse REE contents and trace element concentrations, indicating that the ores underwent differing formation conditions, and the high-grade ores are most likely the reformed product of the original BIFs.The chlorite-quartz schist and amphogneiss are characterized by high SiO₂ and Al₂O₃ contents and exhibit variable abundances of REEs, enrichment in LREEs (light rare earth elements), negative anomalies in HFSEs (e.g., Nb, Ta, P and Ti) and positive anomalies in LILEs (large ion lithophile elements, e.g., Rb, Ba, U and K). A protolith reconstruction indicates that the protoliths of the chlorite-quartz schist are felsic volcanic rocks. SIMS and LA-ICP-MS zircon U–Pb dating indicate that this schist formed at approximately 3110 to 3101 Ma, which could represent the maximum deposition age of the Dagushan BIF. However, two groups of zircons from the amphogneiss are identified: 3104 to 3089 Ma zircons that are most likely derived from the chlorite-quartz schist and 2997 to 2995 Ma zircons, which are interpreted to represent the time of protolith crystallization. Thus, the Dagushan BIF most likely formed before 2997 to 2995 Ma. The ~ 3.1 Ga zircons yield ε_Hf(t) values of − 8.07 to 5.46, whereas the ~ 3.0 Ga zircons yield ε_Hf(t) values of − 3.96 to 2.09. These geochemical features suggest that the primitive magmas were derived from the depleted mantle with significant contributions of ancient crust.     

A review of the genesis of the world class Bayan Obo Fe–REE–Nb deposits,Inner Mongolia,China: Multistage processes and outstanding questions

The Bayan Obo Fe–REE–Nb deposit is the world's largest rare earth element (REE) resource and with the increasing focus on critical metal resources has become a focus of global interest. The deposit is hosted in the Palaeoproterozoic Bayan Obo Group, mainly concentrated in the H8 dolomite marble. The ores consist of light REE enriched monazite and bastnäsite, with a wide array of other REE minerals. Niobium mineralisation is hosted primarily in aeschynite and pyrochlore, although there are a wide range of other Nb-minerals. The origin of the host dolomite and ore bodies has been a subject of intense debate. The host dolomite has been proposed to be both of sedimentary origin and an igneous carbonatite. Carbonatite dykes do occur widely in the area, and consideration of the textural, geochemical and isotopic composition of the dolomite suggests an origin via intrusion of magmatic carbonatite into meta-sedimentary marble, accompanied by metasomatism. The origin of the ore bodies is complex, indicated most strongly by an ~ 1 Ga range in radiometric age determinations. Compilation of available data suggests that the ores were originally formed around 1.3 Ga (Sm–Nd isochron ages; Th–Pb ages of zircon), close in time to the intrusion of the carbonatite dykes. The ores were subsequently subjected to several stages of deformation and hydrothermal overprint, culminating in deformation, metamorphism and fluid flow related to the Caledonian subduction of the Mongolian Plate under the North China Craton from ~ 450 to 420 Ma (Th–Pb ages of monazite). This stage resulted in the formation of the strong foliation (‘banding’) of the ore. The presence of undeformed veins with alkali mineral fills, and the overprinting of the foliation by Nb minerals suggest that secondary fluid flow events may also have contributed to the metal endowment of the deposits, as well as remobilising the original Fe and REE mineralisation. The alteration mineralogy and geochemistry of the ores are comparable to those of many REE mineralised carbonatites. Initial Nd isotope ratios at 450 Ma, however, suggest crustal sources for the metals. These conflicting lines of evidence can be reconciled if a (at least) two stage isotopic evolution is accepted for the deposits, with an original mantle-sourced, carbonatite-related metal accumulation forming around 1.3 Ga with εNd close to 0. The ore was remobilised, with associated re-equilibration of Th–Pb isotope systematics during deformation at ~ 450 Ma. A further stage of alkaline hydrothermal fluid was responsible for Nb mineralisation at this stage. The complex geological history, with multiple stages of alkaline, high field strength element-rich, metasomatic fluid flow, is probably the main reason for the exceptional metal endowment of the Bayan Obo area.     

Distribution of REE,Y, Sc,and Th in the unique complex rare-metal ores of the Tomtor deposit

The REE (Ln), Y, Sc, and Th distribution in the unique complex rare-metal ores of the Tomtor deposit is considered. Significant variability of these components and REE composition is revealed. Ore blocks with elevated Y and HREE contents are identified among prevailing LREE-enriched ores. It is established that the REE variations in the ores are correlated with evolution of REE carriers during epigenetic transformations of the carbonatite weathering products, in particular, with a replacement of Ce-bearing minerals (monazite and florencite) by Y-bearing mineral, xenotime. It is found that LREE and HREE exhibit different behavior during formation of the Tomtor ores, which is expressed in the inert behavior and residual accumulation of Ce-group REE at essential introduction of Y, HREE, Sc, and Th during epigenetic transformation of weathering products of carbonatites, which represent one of the main factors of the formation of the unique rare-metal ores of the Tomtor deposit.     

Polygenesis of mafic-ultramafic complexes: Isotope-geochronological and geochemical evidence from zircons of the Berezovka massif rocks (Sakhalin Island)

Results of comprehensive isotope-geochronological (U-Pb dating; SHRIMP II) and geochemical (LA-ICP-MS) studies of zircons from different rocks of the Berezovka polygenetic mafic-ultramafic massif of the East Sakhalin ophiolite association are presented. The massif includes three proximal but genetically autonomous structure-lithologic complexes of different ages: protrusion of ultramafic rocks of restite nature, gabbroid intrusion breaking through it, and contact reaction zone located along their boundaries. The isotopic age of zircons in the massif as a whole and in its individual rocks varies over a broad range of values. The zircons belong to several populations according to their age (Ma) and other features: relict and xenogenous (~ 3100-990, 70–410, and ~ 395-210) and syngenetic (~ 200-100, ~ 90-65, and ~ 30-20). They differ in grain size and morphology, optical and cathodoluminescence images, and trace-element patterns. By morphology, the grains are divided into short-prismatic crystals with well-developed faces and edges, long-prismatic crystals with well-developed faces and edges, prismatic crystals with slightly resorbed faces and edges, prismatic crystals with strongly resorbed faces and edges, and intensely resorbed grains totally or partly lacking faceting. The ages of zircons depend inversely on the contents of La, Ce, and Yb, total contents of REE, (Ce/Ce*)n, and (Eu/Eu*)n. Some grains are characterized by abnormal REE and trace-element patterns due to their epigenetic redistribution. The wide scatter of the intermediate ages of relict and xenogenous zircon grains, their resorption and disturbed optical and geochemical features are probably due to the nonuniform rejuvenation of their isotope systems and variations in other parameters, caused by the effect of younger mafic melt and its fluids, whose crystallization gave rise to a gabbroid intrusion dated at 170–150 Ma. The obtained data on the isotopic age and other properties of zircons from the rocks of the Berezovka massif agree with the geological model of its polygenesis.     

Evolution of rare-earth mineralization in the Bear Lodge carbonatite,Wyoming: Mineralogical and isotopic evidence

The Bear Lodge alkaline complex in northeastern Wyoming (USA) is host to potentially economic rare-earth mineralization in carbonatite and carbonatite-related veins and dikes that intrude heterolithic diatreme breccias in the Bull Hill area of the Bear Lodge Mountains. The deposit is zoned and consists of pervasively oxidized material at and near the surface, which passes through a thin transitional zone at a depth of ~ 120–183 m, and grades into unaltered carbonatites at depths greater than ~ 183–190 m. Carbonatites in the unoxidized zone consist of coarse and fine-grained calcite that is Sr-, Mn- and inclusion-rich and are characterized by the presence of primary burbankite, early-stage parisite and synchysite with minor bastnäsite that have high (La/Nd)cn and (La/Ce)_cn values. The early minerals are replaced with polycrystalline pseudomorphs consisting of secondary rare-earth fluorocarbonates and ancylite with minor monazite. Different secondary parageneses can be distinguished on the basis of the relative abundances and composition of individual minerals. Variations in key element ratios, such as (La/Nd)_cn, and chondrite-normalized profiles of the rare-earth minerals and calcite record multiple stages of hydrothermal deposition involving fluids of different chemistry. A single sample of primary calcite shows mantle-like δ¹⁸O_V-SMOW and δ¹³C_V-PDB values, whereas most other samples are somewhat depleted in ¹³C (δ¹³C_V-PDB ≈ − 8 to − 10‰) and show a small positive shift in δ¹⁸O_V-SMOW due to degassing and wall-rock interaction. Isotopic re-equilibration is more pronounced in the transitional and oxidized zones; large shifts in δ¹⁸O_V-SMOW (to ~ 18‰) reflect the input of meteoric water during pervasive hydrothermal reworking and supergene oxidation. The textural relations, mineral chemistry and C and O stable-isotopic variations record a polygenetic sequence of rare-earth mineralization in the deposit. With the exception of one Pb-poor sample showing an appreciable positive shift in ²⁰⁸Pb/²⁰⁴Pb value (~ 39.2), the Bear Lodge carbonatites are remarkably uniform in their Nd, Sr and Pb isotopic composition: ¹⁴³Nd/¹⁴⁴Nd_t = 0.512591–0.512608; εNd_t = 0.2–0.6; ⁸⁷Sr/⁸⁶Sr_t = 0.704555–0.704639; εSr_t = − 1.5–2.7; ²⁰⁶Pb/²⁰⁴Pb_t = 18.071–18.320; ²⁰⁷Pb/²⁰⁴Pb_t = 15.543–15.593; and ²⁰⁸Pb/²⁰⁴Pb_t = 38.045–39.165. These isotopic characteristics indicate that the source of the carbonatitic magma was in the subcontinental lithospheric mantle, and modified by subduction-related metasomatism. Carbonatites are interpreted to be generated from small degrees of partial melt that may have been produced via interaction of upwelling asthenosphere giving a small depleted MORB component, with an EM1 component likely derived from subducted Farallon crust.     

Primary and secondary niobium mineral deposits associated with carbonatites

This work reviews the character and origin of primary and supergene economic deposits of niobium associated with carbonatites. The Brazilian supergene deposits account for about 92% of the total worldwide production of Nb, with the primary St. Honoré carbonatite and other sources accounting for only for 7 and 1%, respectively. The emphasis of the review is upon the styles of Nb mineralization and the geological factors which lead to economic concentrations of Nb-bearing minerals. Primary economic deposits of Nb are associated principally with carbonatites found in diverse types of plutonic alkaline rock complexes. Primary magmas are principally those of the melilitite, nephelinite and aillikite clans. Although many primary niobium deposits are associated with carbonatites, ijolites and syenites in the same alkaline complexes can also contain significant Nb mineralization in the form of niobian titanite and diverse Nb–Zr-silicates (marianoite-wöhlerite); these potential sources of Nb have not as yet been explored or exploited. Primary Nb deposits can be regarded as large tonnage, low grade (typically < 1 wt.% Nb₂O₅) disseminated ore deposits. Niobium is hosted principally by diverse Na–Ca–U-pyrochlores, ferrocolumbite and fersmite. Every actual, and potential, primary Nb deposit is unique with respect to the varieties of pyrochlore present; extent of replacement by other minerals; and degree of alteration by deuteric/hydrothermal fluids. Within a given occurrence individual petrographically-defined units of carbonatite contain distinct suites of pyrochlore. Bulk rock analysis for Nb gives no indication of the style of mineralization and provides no information of use regarding beneficiation of the ore. Evaluation of any Nb deposit requires extensive definition drilling and detailed mineralogical studies. Primary Nb deposits result from the early crystallization of Nb-bearing minerals in magma chambers followed by crystal fractionation, magma mixing, and redistribution of Nb-minerals by density currents. Supergene Nb deposits occur in laterites formed by extensive weathering of primary carbonatites. The process results in the decomposition of apatite and magnetite, removal of soluble carbonates and physical concentration of resistant primary pyrochlore. Intense lateritization results initially in the replacement of primary pyrochlores by supergene, commonly Ba, Sr, K or Pb-bearing pyrochlores, and ultimately complete decomposition of pyrochlore and formation of Nb-bearing rutile, brookite, and anatase. The Nb contents of the laterites can be enriched up to 10 times or more above those of the primary carbonatite. Commonly, pyrochlores in laterites are fine grained and intimately intergrown with hematite, goethite and minerals of the crandallite group. The different styles of mineralization of primary and secondary Nb deposits require different methods of ore beneficiation.     

Coexistence of abyssal and ultra-depleted SSZ type mantle peridotites in a Neo-Tethyan Ophiolite in SW Turkey: Constraints from mineral composition,whole-rock geochemistry (major–trace–REE–PGE), and Re–Os isotope systematics

We present new, whole-rock major and trace element chemistry, including rare earth elements (REE), platinum-group elements (PGE), and Re–Os isotope data from the upper mantle peridotites of a Cretaceous Neo-Tethyan ophiolite in the Mu?la area in SW Turkey. We also report extensive mineral chemistry data for these peridotites in order to better constrain their petrogenesis and tectonic environment of formation. The Mu?la peridotites consist mainly of cpx-harzburgite, depleted harzburgite, and dunite. Cpx-harzburgites are characterized by their higher average CaO (2.27 wt.%), Al₂O₃ (2.07 wt.%), REE (53 ppb), and ¹⁸⁷Os/¹⁸⁸Os_(i) ratios varying between 0.12497 and 0.12858. They contain Al-rich pyroxene with lower Cr content of coexisting spinel (Cr# = 13–22). In contrast, the depleted harzburgites and dunites are characterized by their lower average CaO (0.58 wt.%), Al₂O₃ (0.42 wt.%), and REE (1.24 ppb) values. Their clinopyroxenes are Al-poor and coexist with high-Cr spinel (Cr# = 33–83). The ¹⁸⁷Os/¹⁸⁸Os_(i) ratios are in the range of 0.12078–0.12588 and are more unradiogenic compared to those of the cpx-harzburgites.Mineral chemistry and whole rock trace and PGE data indicate that formation of the Mu?la peridotites cannot be explained by a single stage melting event; at least two-stages of melting and refertilization processes are needed to explain their geochemical characteristics. Trace element compositions of the cpx-harzburgites can be modeled by up to ~ 10–16% closed-system dynamic melting of a primitive mantle source, whereas those of the depleted harzburgites and dunites can be reproduced by ~ 10–16% open-system melting of an already depleted (~ 16%) mantle. These models indicate that the cpx-harzburgites are the products of first-stage melting and low-degrees of melt–rock interaction that occurred in a mid-ocean ridge (MOR) environment. However, the depleted harzburgites and dunites are the product of second-stage melting and related refertilization which took place in a supra subduction zone (SSZ) environment. The Re–Os isotope systematics of the Mu?la peridotites gives model age clusters of ~ 250 Ma, ~ 400 Ma and ~ 750 Ma that may record major tectonic events associated with the geodynamic evolution of the Neo-Tethyan, Rheic, and Proto-Tethyan oceans, respectively. Furthermore, > 1000 Ma model ages can be interpreted as a result of an ancient melting event before the Proto-Tethys 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.     

Post-collisional carbonatite-hosted rare earth element mineralization in the Hongcheon area,central Gyeonggi massif,Korea: Ion microprobe monazite U‐Th‐Pb geochronology and Nd‐Sr isotope geochemistry

The Hongcheon area in the central Gyeonggi massif is a unique carbonatite locality in South Korea. The age and petrogenesis of this uncommon rock type and associated rare earth element (REE) mineralization still remain uncertain. The NNE trending, 20–50 m wide and ~ 2 km long Fe-REE ore bodies are hosted within a swarm of carbonatite dykes intruding Precambrian basement gneisses. The intrusive nature of the dykes, fenite alteration halos, exsolution intergrowths of constituent minerals and stable isotope data in the literature collectively attest to the ore formation by crystallization of carbonatite magma. The carbonatites are composed primarily of dolomite, ankerite, siderite, magnetite, monazite, apatite, strontianite and pyrite with subordinate quartz, barite, columbite, fergusonite and calcite. The principal carrier phase of REEs is monazite. The REE contents of monazite vary narrowly (TREO = 66.1–69.4 wt.%) irrespective of the textural occurrence. Although the monazite shows a sample-to-sample variation in La/Nd ratio, the textural varieties from each rock sample are similar with respect to this ratio. Thorium contents in monazite are consistently low (average = ca. 2500 ppm) with unusually high (average = ca. 2200) Th/U ratios. Sensitive high-resolution ion microprobe (SHRIMP) dating of monazite yielded a weighted mean ²⁰⁸Pb/²³²Th age of 232.9 ± 1.6 Ma, which agrees with a weighted mean ²⁰⁶Pb/²³⁸U age of 227.2 ± 8.3 Ma within uncertainties. This age, coupled with comparable intrusion ages documented for kimberlites and monzonite-syenite-gabbro-mangerite suite from central Korea, demonstrates the occurrence of mantle-derived alkaline igneous activities and associated REE mineralization following the North and South China collision. The intrusion of the Hongcheon carbonatite and potassic or ultrapotassic suite in central Korea may have resulted from the post-collisional detachment of the subducted slab and consequent upwelling of hot asthenosphere and melting of the overriding lithospheric mantle. Initial Nd‐Sr isotopic ranges of the Hongcheon carbonatite (ε_Nd = ca. − 26, ⁸⁷Sr/⁸⁶Sr = 0.703–0.706) and previous trace element data deny a petrogenetic linkage with the coeval silicate magmas. The metasomatism in the lithospheric mantle source of the Hongcheon carbonatite must have occurred in the distant past (> 1.7 Ga) to generate significantly negative ε_Nd values.     

In-situ LA-ICP-MS trace elemental analyses of magnetite and Re–Os dating of pyrite: The Tianhu hydrothermally remobilized sedimentary Fe deposit,NW China

The Tianhu Fe deposit (> 104 Mt at 42% TFe) in the Eastern Tianshan (NW China) is hosted in the schist, quartzite, marble, and amphibolite of the Neoproterozoic Tianhu Group. The deposit consists of disseminated, banded and massive ores. Metallic minerals are dominantly magnetite and pyrite, with minor titanite, pyrrhotite, chalcopyrite, and sphalerite. Gangue minerals include dolomite with minor forsterite, diopside, apatite, biotite, chlorite, tourmaline, tremolite, talc, calcite, and magnesite. Pyrite separates from ores have 10.7 to 54.7 ppb Re and 0.033 to 0.175 ppb common Os. Those from the massive ores have a model 1 isochron age of 535 ± 36 Ma (2σ), in agreement with the isochron age (528 ± 18 Ma) of pyrite from the banded ores by regression of seven Re–Os analyses. The Re–Os age of ~ 530 Ma reflects the timing of a hydrothermal event that remobilized the Tianhu deposit. Magnetite has Mg, Al, Ti, V, Mn, Zn, and Ga contents ranging from ~ 5 to 3500 ppm and Cr, Co, Ni, and Sn contents ranging from ~ 1 to 200 ppm. Most magnetite grains have Ca + Al + Mn and Ti + V contents similar to those of the banded iron formation (BIF). Some grains have elevated Ti and V contents, indicating that that magnetite was formed by sedimentary process and overprinted by hydrothermal activity. Pyrite has δ³⁴S_CDT values from − 9.23 to 10.96‰, indicating that the sulfur was reduced from the marine sulfates either by bacterial or thermochemical processes. Pyrite has relatively high Co (~ 346 to 3274 ppm) but low Ni (~ 5.6 to 35.4 ppm) with Co/Ni ratios ranging from ~ 10 to 270, indicating remobilization from a volcanic–hydrothermal fluid. Therefore, the Tianhu Fe deposit was originally a sedimentary type deposit but was overprinted by a hydrothermal event related to volcanic activity.     

Trace elements and Hf isotope composition as indicators of zircon genesis due to the evolution of alkaline-carbonatite magmatic system (Ilmeny-Vishnevogorsky complex,Urals, Russia)

We present results of investigation of the trace-element (REE, HFSE) and Hf isotope compositions and U-Pb age of single zircons crystallized from alkaline-carbonatite magmas of the Ilmeny-Vishnevogorsky complex (IVC) (Urals, Russia). It has been established that the geochemical characteristics of the early zircon (U-Pb age of 430-410 Ma) from alkaline rocks and carbonatites of this complex are determined mainly by the magmatic evolution of parental fluid-saturated alkaline-carbonatite melts and are highly associated with the cocrystallization of zircon and uranium-containing rare-metal minerals (gatchettolite and pyrochlore) at the final stages of the magmatic-system activity. The early zircons have a moderately depleted Hf isotope composition (e_Hf from + 11.3 to + 4.7), confirming the mantle nature of the magma source and indicating the participation of DM-like and enriched-source (probably, lower-crust component) substances in the magma generation. The considerable variations in the initial Hf isotope composition of the early zircons testify to the multistage zircon crystallization involving new portions of melts with different isotope compositions controlled by mixing of substances at their source. Late IVC zircons (250-350 Ma) have strongly disturbed “rejuvenated” isotope systems and a geochemical composition different from that of the magmatic zircons. They formed apparently at the metamorphic stage of the IVC evolution without a significant input of additional material.     

Mineralogical and geochemical studies of brecciated ores in the Dalucao REE deposit,Sichuan Province,southwestern China

The Dalucao deposit, located in western Sichuan Province, southwestern China, in the western part of the Yangtze Craton, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE belt. Moreover, the Dalucao deposit is the only deposit identified in the southern part of the belt. The Dalucao deposit contains the No. 1, 2, and 3 orebodies; the No. 1 and 3 orebodies are both hosted in two breccia pipes, located in syenite–carbonatite host rocks. Both pipes have elliptical cross-sections at the surface, with long-axis diameters of 200–400 m and short-axis diameters of 180–200 m; the pipes extend downwards for > 450 m. No. 1 and No. 3 have total thickness varying between 55 and 175 m and 14 to 58 m respectively. The REE mineralization is associated with four brecciation events, which are recorded in each of the pipes. The ore grades in the No. 1 and 3 orebodies are similar, and consist of 1.0%–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a Type I mineral assemblage (fluorite + barite + celestite + bastnäsite), whereas the No. 3 orebody is characterized by a Type II assemblage (fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite). Argon (⁴⁰Ar/³⁹Ar) dating of hydrothermal muscovite intergrown with REE minerals in typical ores from the No. 1 and 3 orebodies yielded similar ages of 12.69 ± 0.13 and 12.23 ± 0.21 Ma, respectively, which suggest that both mineral assemblages formed coevally, rather than in paragenetic stages. Both ages are also similar to the timing of intrusion of the syenite–carbonatite complex (12.13 ± 0.19 Ma). The ore-mineral assemblages occur in breccias, veinlets, and in narrow veins. The ore veinlets, which usually show a transition to mineralized breccia or brecciated ores, are commonly enveloped by narrow veins and stringer zones with comparable mineral assemblages. The brecciated ores form 95% of the volume of the deposit, whereas brecciated ores are only a minor constituent of other deposits in the Mianning–Dechang REE belt. The carbonatite in the syenite–carbonatite complexes contains high concentrations of S (0.07–2.32 wt.%), Sr (16,500–20,700 ppm), Ba (3600–8400 ppm), and light REEs (LREE) (2848–10,768 ppm), but is depleted in high-field-strength elements (HFSE) (Nb, Ta, P, Zr, Hf, and Ti). The syenite is moderately enriched in large-ion lithophile elements (LILE), Sr (155–277 ppm), and Ba (440–755 ppm). The mineralized, altered, and fresh syenites and carbonatites exhibit similar trace element compositions and REE patterns. Brecciation events, and the Dalucao Fault and its secondary faults around the deposit, contributed to the REE mineralization by facilitating the circulation of ore-forming fluids and providing space for REE precipitation. Some hydrothermal veins composed of coarse-grained fluorite and quartz are distributed in the syenite–carbonatite complex. The oxygen isotope compositions of ore-forming fluids in equilibrium with quartz at 215 °C are − 4.95‰ to − 7.45‰, and the hydrogen isotope compositions of fluid inclusions in coarse-grained quartz are − 88.4‰ to − 105.1‰. The syenite–carbonatite complex and carbonatite are main contributors to the mineralization in the geological occurrence. Thus, the main components of the ore-forming fluids were magmatic water, meteoric water, and CO₂ derived from the decarbonation of carbonatite. According to the petrographic studies, bastnäsite mineralization developed during later stages of hydrothermal evolution and overprinted the formation of the brecciated fluorite–quartz hydrothermal veins. As low-temperature isotope exchange between carbonates of the carbonatite and water-rich magmatic fluids will lead to positive shifts in δ¹⁸O values of the carbonates, C–O isotopic compositions from the bulk primary carbonatite to hydrothermal calcite and bastnäsite changed (δ¹⁸O_V-SMOW from 8.0‰ to 11.6‰, and δ¹³C _V-PDB from − 6.1 to − 8.7‰). According to the chemical composition of syenite and carbonatite, REE chloride species are the primary complexes for the transport of the REEs in the hydrothermal fluids, and the presence of bastnäsite and parisite means the REE were precipitated as fluorocarbonates. High contents of Sr, Ba and S in the syenite–carbonatite complex led to the deposition of large amount of barite and celestite.     

Geochemical and mineralogical characteristics of weathered ore in the Dalucao REE deposit,Mianning–Dechang REE Belt,western Sichuan Province,southwestern China

The Dalucao deposit in western Sichuan Province, southwest China, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE Belt. Moreover, this is the only deposit identified in the southern part of the belt. The deposit contains the No. 1, 2, and 3 orebodies. The No. 1 and 3 orebodies are hosted in two breccia pipes within syenite–carbonatite rocks that intrude a Proterozoic quartz–diorite pluton. Both breccia pipes have elliptical horizontal cross-sections at the surface, being 200–400 m long, 180–200 m wide, and extending to > 450 m depth. The No. 1 and No. 3 orebodies have total thicknesses of 55–175 m and 14–58 m, respectively. REE mineralization is associated with four brecciation events that are recorded in both pipes. The ore grades in the No. 1 and 3 orebodies are similar, with the rocks containing 1.0–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a mineral assemblage comprising fluorite + barite + celestite + bastnäsite (i.e., Type I), whereas the No. 3 orebody is characterized by an assemblage comprising fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite (i.e., Type II). Significant amounts of weathered high-grade REE ore (up to 60 wt.% of the rock mass) is mainly present in the No. 1 orebody. This is the main ore-type targeted for exploration within the Dalucao deposit, but is rarely present in other deposits in the Mianning–Dechang REE Belt.Faulting and cryptoexplosive breccia events, possibly linked to movement on the Panxi Fault, were more common in the No. 1 orebody than in the No. 3 orebody. This facilitated the introduction of ore-forming hydrothermal fluids and provided space for the precipitation of REE minerals. Based on the present results, we infer that the Dalucao deposit was the product of multiple stages of ore formation. REE minerals formed in envelopes around, or fractures within, quartz, fluorite, calcite, barite, and celestite in the brecciated ores. The main REE minerals were deposited from hydrothermal fluids within cryptoexplosive breccia, followed by weathering that increased the ore grade. Petrographic studies and X-ray powder diffraction (XRD) analyses indicate that the weathered ore contains 5–60% REE minerals (including bastnäsite, parisite, and monazite), together with gangue (quartz, barite, celestite, and fluorite), large amount of clay minerals (smectite, illite, kaolinite, and sepiolite), and relict igneous minerals (quartz, albite, and K-feldspar). The weathered samples are strongly enriched in La (up to 92,390 ppm), Ce (up to 103,500 ppm), Pr (up to 8006 ppm), and Nd (up to 16,690 ppm) compared with the unweathered brecciated ores. Conversely, Sr concentrations are significantly more enriched in the brecciated ores (up to 256,500 ppm) than in the weathered ores (generally less than 2671 ppm with one exception of 37,850 ppm) due to less celestite. Calcite is largely absent from the weathered ores (except one sample with up to 30% mode), which contrasts with the brecciated ores that contain up to 75% calcite. The effects of weathering, oxidation, loss of ions, and hydration on the brecciated ores led to the refertilization of the REEs and an increase in the grade of the ore deposit.