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.     

Dolomite-calcite textures in early carbonatites of the Kovdor ore deposit,Kola peninsula,Russia: their genesis and application for calcite-dolomite geothermometry

In early calcite carbonatites of the Kovdor ore deposit four morphological types of dolomite are represented. In the first type, dolomite microcrystals occur as lamellae enclosed by optically continuous calcite. In the second, dolomite microcrystals occur as segmented rods, plates and xenomorphic grains, enclosed by optically discontinuous calcite, and in the third, dolomite is represented by grains of various morphologies, situated along calcite grain boundaries. The fourth type of dolomite occurs as a fine-grained aggregate, which develops along grain boundaries and cleavage cracks of calcite. From microscopic, scanning electron microscope and microprobe studies of these different types of dolomite microcrystals, as well as the calcite associated with them, it can be concluded that the first type of dolomite was exsolved from magnesian calcite during cooling. The second, and the third types of dolomite microcrystals were formed by recrystallization. The fourth type of dolomite was formed by metasomatic dolomitization. As the result of these two processes-recrystallization and metasomatic dolomitization-early dolomite microcrystals seldom occur. The composition of the early-formed primary magnesian calcite yielded temperatures of exsolution of dolomite from magnesian calcite between 665 and 700°C.     

Nd and Sr isotope signatures of the Khibina and Lovozero agpaitic centres, Kola Alkaline province, Russia

Nd and Sr compositions of the highly evolved agpaitic nepheline syenites and associated ijolites and carbonatites from the Khibina and the Lovozero alkaline centres define three magma sources. Isotopes of the voluminous nepheline syenites and ijolites of Khibina intrusions III, IV, V, VI and VII as well as of nepheline syenites of Lovozero lie on the Kola Carbonatite Mixing Line which is close to the “mantle array” defined by the components “bulk earth” and “prema” on a Sr---Nd plot. The Khibina carbonatites and associated silicate rocks of intrusion VIII, which have more radiogenic Sr, did not evolve from the same parent magma as the nepheline syenites.

Isotopic constraints exclude a pre-enrichment of Rb, Sr, Sm and Nd in the lithospheric mantle below Kola over more than 10 Ma prior to the crystallization of the magmas. A formation of the melts involving major participation of the Precambrian crust of the Baltic Shield is also excluded.

The lack of significant Eu anomalies in the Lovozero nepheline syenites gives evidence that the agpaitic magmas in the Kola region did not form from basaltic liquids by fractional crystallization of plagioclase or anorthoclase at crustal levels. A formation from nephelinite or nepheline benmoreite magmas at mantle pressures is more likely, possibly by dynamic flow crystallization.

Enrichment factors suggest that large-ion lithophile and high field-strength elements as Ta, La, Nb and Zr, which are highly concentrated in the agpaites, were scavenged from mantle volumes of some 100,000 km³. An enrichment of these elements prior to magma formation may have been performed by volatile transfer.

The well-defined whole-rock isochrons of the Khibina III–VII and the Lovozero agpaites of c. 370 Ma date the magma separation for the different intrusion, if these melts are cogenetic and formed by fractional crystallization in a Khibina and a Lovozero magma chamber. If, however, Rb and Sr were collected by a process of volatile transfer, and the initial Sr isotopic compositions of the two distinguished agpaite suites are, therefore, averages of the sampled mantle volumes, the Rb---Sr whole-rock isochron ages of c. 370 Ma would date this process of element collection. The concordance of the whole-rock ages with the mineral ages of Khibina and Lovozero samples is then further evidence for the short period between magma genesis, intrusion and crystallization.     

The formation conditions of labuntsovite-group minerals in the Kovdor massif,Kola Peninsula

In the Kovdor massif, labuntsovite-group minerals occur in dolomite carbonatite veins (labuntsovite-Mg), in a natrolite-calcite vein (lemmleinite-Ba and labuntsovite-Fe), and in calcite pockets and veinlets cutting fenites (late labuntsovite-Mg). They are closely intergrown with paragenetic carbonates, and this makes it possible to estimate their crystallization temperature from the fluid inclusions entrapped in dolomite (≥265°C) and calcite (175–225°C). The earlier labuntsovite-Mg was formed under relatively acidic conditions, whereas later labuntsovite-calcite mineralization was derived from alkaline solutions.     

Evolution of chemical composition of pyrochlore group minerals from phoscorites and carbonatites of the Khibina alkaline massif

Phoscorites and carbonatites of the Khibina alkaline massif, Russia contain three minerals of the pyrochlore group. They are, in order of crystallization: uranpyrochlore and pyrochlore in the phoscorites, and pyrochlore and bariopyrochlore in late calcite carbonatites. Early calcite carbonatites also contain uranpyrochlore and pyrochlore, but they are xenocrysts derived from the phoscorites. Alteration of the pyrochlore group minerals led to increasing U, Ti and water contents and decreasing Na, Ca, Nb and F contents. Crystallization of zoned uranpyrochlore to pyrochlore crystals in the phoscorites is explained by the experiments of Ryabchikov and Hamilton (1993, 1994) on the interaction of carbonate-phosphate melts with mantle peridotites.     

Isotopic composition of Sr,Nd, and Pb in pirssonite,shortite and calcite carbonatites from Oldoinyo Lengai volcano,Tanzania

Doklady Earth Sciences -     

Britholite-group minerals as sensitive indicators of changing fluid composition during pegmatite formation: evidence from the Keivy alkaline province,Kola peninsula,NW Russia

Mineralogy and Petrology - The Keivy alkaline province, Kola Peninsula, NW Russia, consists of vast alkali granite massifs and several dike-like nepheline syenite bodies. It contains numerous...     

Sr and Nd isotope data from the fluorspar district of Asturias, northern Spain

The origin and age of the hydrothermal fluids related to the precipitation of fluorite, barite and calcite in the Villabona, La Collada and Berbes localities (Asturias fluorspar district, N Spain) have been evaluated from Sr and Nd radiogenic isotopes. Sr isotope data (⁸⁷Sr / ⁸⁶Sr = 0.7081 to 0.7096) are compatible with mixing between seawater and a more evolved groundwater that interacted with the basement. From Nd isotopes in fluorite, an isochron age of 185 ± 29 Ma (Lower Jurassic) was obtained, consistent with other hydrothermal events in the Iberian Peninsula and Europe. These constraints are essential to proceed with a quantitative model for the genesis of the mineralization that includes fluid and heat flow together with reactive transport of solutes.     

Light noble gas data in Guli massif carbonatites reveal the subcontinental lithospheric mantle as primary fluid source

For better understanding of the fluid phase sources of carbonatites of Guli alkaline-ultrabasic intrusion (Maymecha-Kotuy complex) we have studied isotope composition of He and Ne in the carbonatites of different formation stages. The data definitely point to the subcontinental lithospheric mantle (SCLM) as a primary source of fluid phase of Guli carbonatites. The absence of plume signature in such a plume-like object (from petrological point of view) could be explained in terms that Guli carbonatites have been formed at the waning stage of plume magmatic activity with an essential input of SCLM components.     

Geochemistry and age of the complex of alkaline metasomatic rocks and carbonatites of the Gremyakha-Vyrmes massif, Kola Peninsula

This paper presents new geochemical data on the complex of alkaline metasomatic rocks and carbonatites, which hosts the rare-metal mineralization of the Gremyakha-Vyrmes massif. The contents of major and trace, including rare-earth elements were determined in the albitites, aegirinites, and carbonatites. Two types of the rare-metal ores are distinguished: niobium albitite and zirconium aegirinite ores. It was shown that the albitites and aegirinites have similar trace element distribution patterns, being most geochemically close to the foidolites. The carbonatites, albitites, and aegirinites were dated by Rb-Sr and Sm-Nd methods at 1887 ± 58 Ma, which corresponds to the formation age of the Gremyakha-Vyrmes massif. The ultrabasic rocks, foidolites, alkaline metasomatic rocks, and carbonatites were formed successively within a relatively narrow range. The geological observations and geochemical data led us to conclude that the emplacement of the fluid-saturated carbonatite solutions-melts at the final stages of the massif formation against a background of fault tectonics caused a pervasive metasomatism of the ultrabasic and alkaline rock complexes and, as a result, the formation of the alkaline albitites and aegirinites. The carbonatites could be sources of rare-metals, while foidolites served as a geochemical barrier, and their metasomatic alteration led to the formation of Zr-Nb mineralization in the albitites and aegirinites.     

Plume-related mantle source of super-large rare metal deposits from the Lovozero and Khibina massifs on the Kola Peninsula, Eastern part of Baltic Shield: Sr, Nd and Hf isotope systematics

The two world’s largest complexes of highly alkaline nepheline syenites and related rare metal loparite and eudialyte deposits, the Khibina and Lovozero massifs, occur in the central part of the Kola Peninsula. We measured for the first time in situ the trace element concentrations and the Sr, Nd and Hf isotope ratios by LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometer) in loparite, eudialyte an in some other pegmatitic minerals. The results are in aggreement with the whole rock Sr and Nd isotope which suggests the formation of these superlarge rare metal deposits in a magmatic closed system. The initial Hf, Sr, Nd isotope ratios are similar to the isotopic signatures of OIB indicating depleted mantle as a source. This leads to the suggestion that the origin of these gigantic alkaline intrusions is connected to a deep seated mantle source—possibly to a lower mantle plume. The required combination of a depleted mantle and high rare metal enrichment in the source can be explained by the input of incompatible elements by metasomatising melts/fluids into the zones of alkaline magma generation shortly before the partial melting event (to avoid ingrowth of radiogenic isotopes). The minerals belovite and pyrochlore from the pegmatites are abnormally high in ⁸⁷Sr /⁸⁶Sr ratios. This may be explained by closed system isotope evolution as a result of a significant increase in Rb/Sr during the evolution of the peralkaline magma.     

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 and geochemistry of silicate dyke rocks associated with carbonatites from the Khibina complex (Kola, Russia) – isotope constraints on genesis and small-scale mantle sources

Summary The eastern part of the agpaitic Khibina complex is characterized by the occurrence of dykes of various alkali silicate rocks and carbonatites. Of these, picrite, monchiquite, nephelinite and phonolite have been studied here. Whole rock and mineral geochemical data indicate that monchiquites evolved from a picritic primary magma by olivine+ magnetite fractionation and subsequent steps involving magma mixing at crustal levels. None of these processes or assimilation/magma mixing of wall rocks or other plutonic rocks within the complex can entirely explain the geochemical and Nd–Sr-isotopic characteristics of the monchiquites (i.e. a covariant alignment between (⁸⁷Sr/⁸⁶Sr)₃₇₀=0.70367, (¹⁴³Nd/¹⁴⁴Nd)₃₇₀=0.51237 and (⁸⁷Sr/⁸⁶Sr)₃₇₀=0.70400, (¹⁴³Nd/¹⁴⁴Nd)₃₇₀=0.51225 representing the end points of the array). This signature points to isotopic heterogeneities of the mantle source of the dyke-producing magma. The four mantle components (i.e. depleted mantle, lower mantle plume component, EMI-like component and EMII-like component) must occur in different proportions on a small scale in order to explain the isotopic variations of the dyke rocks. The EMII-like component might be incorporated into the source area of the primary magma by carbonatitic fluids involving subducted crustal material. The most likely model to explain the small-scale isotopic heterogeneity is plume activity. The results of this study do not provide any support to a cogenetic origin (e.g. fractionation or liquid immiscibility) for carbonatite and monchiquite or other alkali-silicate dyke rocks occurring in spatial proximity. Instead, we propose that both, carbonatite and picrite/monchiquite, originated by low-degree partial melting of peridotite. Textural observations, mineralogical data, and C and O isotopic compositions suggest incorporation of calcite from carbonatite in monchiquite and the occurrence of late-stage carbothermal fluids.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s00710-003-0016-2     

Age and provenance of early Precambrian metasedimentary rocks in the Lapland–Kola Belt, Russia: evidence from Pb and Nd isotopic data

²⁰⁷Pb/²⁰⁶Pb ages are presented for detrital zircons (Laser Ablation Microprobe ICP‐MS) and whole‐rock Nd isotopic determinations (TIMS) from samples of Neoarchean and Palaeoproterozoic metasedimentary rocks from the Umba granulite terrane and the Keivy domain of the Central Kola composite terrane, Kola Peninsula, north‐western Russia. Three are samples of rocks from the Umba granulite terrane that were deposited ≈ 2.20–1.90 Ga; they contain Archaean detritus, much of it older than 3.0 Gyr, as well as abundant 2.20–1.95‐Gyr‐old material. Deposition may have occurred on the margin of an Archaean craton with an exposed Palaeoproterozoic magmatic arc source, possibly during orogenesis. Two samples from the Keivy domain have remarkably similar, dominantly Archaean detrital zircon age spectra. One was deposited pre‐2.4 Ga, whereas the other was probably deposited post‐2.01 Ga. Both had similar sources, compatible with the proximal country rocks, and possible shallow‐water (?) cratonic margin depositional settings.     

Oxygen isotope evolution of biogenic calcite and apatite during the Middle and Late Devonian

Oxygen isotope ratios of well-preserved brachiopod calcite and conodont apatite were used to reconstruct the palaeotemperature history of the Middle and Late Devonian. By assuming an oxygen isotopic composition of –1 V-SMOW for Devonian seawater, the oxygen isotope values of Eifelian and early Givetian brachiopods and conodonts give average palaeotemperatures ranging from 22 to 25 °C. Late Givetian and Frasnian palaeotemperatures calculated from ¹⁸O values of conodont apatite are close to 25 °C in the early Frasnian and increase to 32 °C in the latest Frasnian and early Famennian. Oxygen isotope ratios of late Givetian and Frasnian brachiopods are significantly lower than equilibrium values calculated from conodont apatite ¹⁸O values and give unrealistically warm temperatures ranging from 30 to 40 °C. Diagenetic recrystallization of shell calcite, different habitats of conodonts and brachiopods, as well as non-equilibrium fractionation processes during the precipitation of brachiopod calcite cannot explain the ¹⁸O depletion of brachiopod calcite. Moreover, the ¹⁸O depletion of brachiopod calcite with respect to equilibrium ¹⁸O values calculated from conodont apatite is too large to be explained by a change in seawater pH that might have influenced the oxygen isotopic composition of brachiopod calcite. The realistic palaeotemperatures derived from ¹⁸O _apatite may suggest that biogenic apatite records the oxygen isotopic composition and palaeotemperature of Palaeozoic oceans more faithfully than brachiopod calcite, and do not support the hypothesis that the ¹⁸O/¹⁶O ratio of Devonian seawater was significantly different from that of the modern ocean.     

A Pb isotope investigation of the Lovozero Agpaitic Nepheline Syenite,Kola Peninsula,Russia

For the first time Pb isotope composition was established in Lovozero rocks and raremetal ores, which is important for identifying their sources. The world’s largest layered intrusion of agpaitic nepheline syenite-the Lovozero alkaline massif—is located near the center of the Kola Peninsula in Russia. This superlarge complex plutonic body hosts the economically important loparite and eudiallyte deposits [1]. These deposits contain immense resources of REE, Nb, Ta, Zr, and constitute a world class mineral district. The Lovozero massif belongs to the Kola ultramafic alkaline and carbonatitic province (KACP) of Devonian age. Previous bulk rock studies have shown that the initial Sr and Nd isotope ratios of Lovozero rocks plot in the depleted mantle quadrant of Sr-Nd diagrams [2]. More recently, Hf isotope data obtained by Kogarko et al. (3) confirm that the Lovozero and Khibina massifs with ?_Hf between 6 and 8 are derived predominantly from a depleted mantle source. It was shown that Sr, Nd, and Hf abundances are significantly elevated in the Kola alkaline rocks, and thus their isotopic compositions are relatively insensitive to minor contamination by the overlying crustal rocks. By contrast, Pb in the KACP rocks is a much more sensitive indicator of a crustal component. In this paper we investigate the lead isotopic signature of all resentative types of Lovozero rocks (Table 1) in order to further characterize their mantle sources. The Lovozero massif consists of four intrusive phases. Rocks of phase I (mostly nepheline syenites) comprise about 5% of the total volume, phase II (urtites, foyaite, lujavrites) forms the main portion of the massif comprising 77% in volume, and phase III (eudialyte lujavrites) contributes about 18%. Country rocks are represented by Devonian effusive rocks and Archean gneisses.