On the geochemistry of tantalum in the carbonatite process

The behavior of tantalum in carbonatites and related rocks of alkaline complexes was analyzed. In particular, we considered factors favorable for its accumulation in carbonatites, both in absolute amount and relative to its companion element niobium.The contents of both elements show moderate variations in earlier alkaline silicate rocks and more significant variations in carbonatites; this difference is especially pronounced for tantalum.Their simultaneous accumulation in carbonatites is controlled mainly by the affiliation to certain temperature facies, when tantalate-niobate phases with high Ta₂O₅ contents (up to 26 wt %) are formed. The accumulation of these elements with the formation of almost purely niobian pyrochlores and Ta-U pyrochlores (hatchettolites) occurs efficiently only during the formation of metasomatic zoning with the separation of purely Nb and Nb-Ta mineralization between the zones of the metasomatic column. This process is characteristic mainly of relatively deep-seated massifs, where the metasomatic processes of carbonatite formation are dominant, at least for the given temperature facies.     

New data on carbonatites of the Il’mensky-Vishnevogorsky alkaline complex,the southern Urals,Russia

Carbonatites that are hosted in metamorphosed ultramafic massifs in the roof of miaskite intrusions of the Il’mensky-Vishnevogorsky alkaline complex are considered. Carbonatites have been revealed in the Buldym, Khaldikha, Spirikha, and Kagan massifs. The geological setting, structure of carbonatite bodies, distribution of accessory rare-metal mineralization, typomorphism of rock-forming minerals, geochemistry, and Sr and Nd isotopic compositions are discussed. Dolomite-calcite carbonatites hosted in ultramafic rocks contain tetraferriphlogopite, richterite, accessory zircon, apatite, magnetite, ilmenite, pyrrhotite, pyrite, and pyrochlore. According to geothermometric data and the composition of rock-forming minerals, the dolomite-calcite carbonatites were formed under K-feldspar-calcite, albite-calcite, and amphibole-dolomite-calcite facies conditions at 575–300°C. The Buldym pyrochlore deposit is related to carbonatites of these facies. In addition, dolomite carbonatites with accessory Nb and REE mineralization (monazite, aeschynite, allanite, REE-pyrochlore, and columbite) are hosted in ultramafic massifs. The dolomite carbonatites were formed under chlorite-sericite-ankerite facies conditions at 300–200°C. The Spirikha REE deposit is related to dolomite carbonatite and alkaline metasomatic rocks. It has been established that carbonatites hosted in ultramafic rocks are characterized by high Sr, Ba, and LREE contents and variable Nb, Zr, Ti, V, and Th contents similar to the geochemical attributes of calcio-and magnesiocarbonatites. The low initial ⁸⁷Sr/⁸⁶Sr = 0.7044?0.7045 and εNd ranging from 0.65 to ?3.3 testify to their derivation from a deep mantle source of EM₁ type.     

Hot-fluid Driven Metasomatism of Samalpatti Carbonatites, South India: Evidence from Petrology, Mineral Chemistry, Trace Elements and Stable Isotope Compositions

The magmatic heritage of carbonatites can be identified on the basis of a combination of geological criteria such as, their mode of occurrence, the nature of associated igneous rocks, the presence of minerals of igneous origin, fenitization, characteristic trace element contents and isotopic composition. Late Proterozoic Samalpatti carbonatites were studied in view of these criteria, and were found to contain metamorphic minerals that normally form under thermal metamorphic conditions and which have unusual chemical compositions. A combination of criteria points clearly to a magmatic origin for these carbonatites. Field relations indicate that the dominant modes of intrusion of carbonatite into the encompassing pyroxenites and syenites include small dykes, veins, or lenses. The igneous nature of these carbonatites has been described elsewhere and chemically they are classified as calico-carbonatites. Currently, very little is known about the metamorphic textures and mineralogy observed in the Samalpatti carbonatites. In this study, several metamorphic minerals are reported including diopside, grossularite, vesuvianite, K-feldspar and wollastonite, and a hornfelsic texture is described. These mineral phases and texture characterize thermal metamorphism under low pressure and high temperature (LP-HT) metamorphic conditions (650°_750°C) or metasomatism aided by hot-fluid advection. The metamorphic nature of minerals reported is also confirmed by electron microprobe study. The Samalpatti carbonatite samples show much lower values of characteristic trace elements (P, Sr, Ba, Zr, Nb, Th, Y and REEs) than average concentrations for magmatic carbonatite. Stable isotopic (d¹³C and d¹⁸O) compositions of Samalpatti carbonatites do not fall in the primary igneous carbonatite (PIC) domain. The petrological and chemical signatures of these carbonatites suggest metasomatism in conjunction with fluid advection. Such a metasomatic process may drastically change the chemistry of the rocks in addition to enrichment of heavier stable isotopes. During this metasomatic process, characteristic elements would be dissolved in the high d¹⁸O fluid, and together with Rayleigh fractionation would contribute to enhanced concentrations of ¹³C and ¹⁸O in Samalpatti carbonatites.     

Metasomatic processes in the lithospheric mantle beneath the V. Grib kimberlite pipe (Arkhangelsk diamondiferous province,Russia)

New data on metasomatic processes in the lithospheric mantle in the central part of the Arkhangelsk diamondiferous province (ADP) are presented. We studied the major- and trace-element compositions of minerals of 26 garnet peridotite xenoliths from the V. Grib kimberlite pipe; 17 xenoliths contained phlogopite. Detailed mineralogical, petrographic, and geochemical studies of peridotite minerals (garnet, clinopyroxene, and phlogopite) have revealed two types of modal metasomatic enrichment of the lithospheric-mantle rocks: high temperature (melt) and low-temperature (phlogopite). Both types of modal metasomatism significantly changed the chemical composition of the peridotites. Low-temperature modal metasomatism manifests itself as coarse tabular and shapeless phlogopite grains. Two textural varieties of phlogopite show significant differences in chemical composition, primarily in the contents of TiO₂, Cr₂O₃, FeO, Ba, Rb, and Cs. The rock-forming minerals of phlogopite-bearing peridotites differ in chemical composition from phlogopite-free peridotites, mainly in higher FeO content. Most garnets and clinopyroxenes in peridotites are the products of high-temperature mantle metasomatism, as indicated by the high contents of incompatible elements and REE pattern in these minerals. Fractional-crystallization modeling gives an insight into the nature of melts (metasomatic agents). They are close in composition to picrites of the Izhmozero field, basalts of the Tur’ino field, and carbonatites of the Mela field of the ADP. The REE patterns of the peridotite minerals make it possible to determine the sequence of metasomatic enrichment of the lithospheric mantle beneath the V. Grib kimberlite pipe.     

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.     

Geochemical typification of kimberlite and related rocks of the North Anabar region,Yakutia

The results of geochemical typification of kimberlites and related rocks (alneites and carbonatites) of the North Anabar region are presented with consideration of the geochemical specification of their source and estimation of their potential for diamonds. The content of representative trace elements indicates the predominant contribution of an asthenospheric component (kimberlites and carbonatites) in their source, with a subordinate contribution of vein metasomatic formations containing Cr-diopside and ilmenite. A significant contribution of water-bearing potassium metasomatic parageneses is not recognized. According to the complex of geochemical data, the studied rocks are not industrially diamondiferous.     

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.     

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.     

Phlogopite-biotite parageneses from the K-mafic-carbonatite effusive magmatic association of Katwe-Kikorongo, SW Uganda

Summary Ti-bearing phlogopite-biotite is dominant in Ugandan kamafugite-carbonatite effusives and their entrained alkali clinopyroxenite xenoliths. It occurs as xeno/phenocrysts, microphenocrysts and groundmass minerals and also as a major xenolith mineral. Xenocrystic micas in kamafugites and carbonatites are aluminous (> 12 wt% Al₂O₃), typically contain significant levels of Cr (up to 1.1 wt% Cr₂O₃), and are Ba-poor. Microphenocryst and groundmass micas in feldspathoidal rocks extend to Al-poor compositions, are depleted in Cr, and are generally enriched in Ba. In general, xenocrystic micas occupy the Al₂O₃ and TiO₂ compositional field of the xenolith mica, and on the basis of Mg#, and high P, T experimental evidence they probably crystallised at mantle pressures. Mica xenocryst Cr contents range from those in Cr-poor megacryst and MARID phlogopite to higher values found in primary and metasomatic phlogopites in kimberlite-hosted peridotite xenoliths. Such Cr contents in Ugandan mica xenocrysts are considered consistent with derivation from carbonate-bearing phlogopite wehrlite and phlogopite-clinopyroxenite mantle. Olivine melilitite xenocryst micas are distinguished by higher Mg# and Cr content than mica in clinopyroxenite xenoliths and mica in Katwe-Kikorongo mixed melilitite-carbonatite tephra. Higher Al₂O₃ distinguishes Fort Portal carbonatite xenocrysts and some contain high Cr. It is suggested that the genesis of Katwe-Kikorongo olivine melilitite and Fort Portal carbonatite involves a carbonate-bearing phlogopite wehrlite source while the source of the mixed carbonatite-melilitite rocks may be carbonate-bearing phlogopite clinopyroxenite. Received January 24, 2000; revised version accepted September 27, 2001     

Micas from the Khaluta carbonatite deposit,western Transbaikal region

The Khaluta carbonatite deposit located in the western Transbaikal region was formed during the Late Mesozoic rifting in the southern framework of the Siberian Craton. Carbonatite is associated with shonkinite and syenite and is accompanied by fenitization. The composition of mica in more than 160 samples of country rocks, carbonatites, silicate rocks, and fenites was studied. The Fe³⁺ and Fe²⁺ contents, as well as oxygen isotopic composition, were determined. The Mg and Fe contents increase, whereas the Ti and Al contents decrease in micas when passing from silicate rocks and fenites to carbonatites. Micas from carbonatites are depleted in Al, enriched in Fe³⁺, and distinguished by high Si and F contents. According to our calculations, in some cases Al replaces Si in the tetrahedral site instead of replacement of Fe³⁺ as is characteristic of tetraferriphlogopite. Formally, the mica from carbonatites falls within the tetraferriphlogopite field, but typical inverse pleochroism is not always observable. The δ¹⁸O values of micas from carbonatite, shonkinite, syenite, and fenite are similar to those of mantle-derived silicate minerals. The δ¹⁸O values in the minerals coexisting with phlogopite testify to their isotopic equilibrium and make it possible to calculate the crystallization temperature of carbonatite.     

Non-magmatic Features in Carbonatitic Rocks: A Re-examination of Proterozoic “Carbonatites,” Southeast Rajasthan,Northwest Indian Craton

The Newania carbonatitic rocks (NCB), exposed as NW-trending, isolated linear bodies within Archean granitoids, are comprised mainly of Mg- and Fe-carbonate phases and volumetrically negligible Ca carbonate. The magmatic Mg-carbonatite shows partial metasomatic replacement by iron-rich solutions channelized along fractures. The C- and 0-isotopic compositions further document the magmatic lineage of the Mg-carbonatite (δ¹³C_PDB = ?4.0 to ?5.9% and δ¹⁸ O_SMOW = + 8.2 to 11.5%, barring one sample characterized by a high value of +25.6%). In contrast, the presumed ankeritic (Fe) and sovitic (Ca) carbonatites appear to be the result of metasomatism and hydrothermal activity, as indicated by corresponding enrichment in the heavier isotopes. The “atypical carbonatites” of Nayaphala, occurring as NW-trending dikes and veins of variable width (south of and colinear with the Newania trend), are nonmagmatic, and can be described as tectonic breccias. A nonmagmatic source for Nayaphala carbonates also is supported by the corresponding enrichment in the heavier C and O isotopes.     

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 alleged kimberlite-carbonatite relationship: evidence from ilmenite and spinel from Premier and Wesselton mines and the Benfontein sill,South Africa

Carbonate-rich, SiO₂-poor residua are developed in some kimberlites solidifying as ocelli, layers, or discrete dikes which satisfy petrographic definitions of carbonatite. Arguments that these rocks have mineralogies, antecedents, and comagmatic rocks differing from those of the carbonatites in alkaline rock complexes, including the specific observation that kimberlites and carbonatites contain ilmenites and spinels of different composition, have been used to refute the alleged kimberlite-carbonatite relationship. New microprobe analyses of ilmenites and spinels from carbonate-rich rocks associated with kimberlites in three South African localities correspond to spinels and ilmenites of carbonatites from alkalic complexes, or have characteristics intermediate between those of carbonatites and kimberlites. The ilmenites are distinguished from kimberlite ilmenites by higher MnO, FeTiO₃, and Nb₂O₅, and by negligible Cr₂O₃. The spinels are distinguished from kimberlite spinels by their Al₂O₃ and Cr₂O₃ contents. There is clearly a genetic relationship between the kimberlites and the carbonate-rich rocks, despite the observation that their ilmenites and spinels are distinctly different, which indicates that the same observation is not a valid argument against a petrogenetic relationship between kimberlites and carbonatites. These rocks are among the diverse products from mantle processes influenced by CO₂, and we believe that the petrogenetic links among them are forged in the upper mantle. We see insufficient justification to deny the name carbonatite to carbonate-rich rocks associated with kimberlites if they satisfy the petrographic definition in terms of major mineralogy.     

Metasomatic effects related to channelled fluid streaming through deep crust: fenites and associated carbonatites (In Ouzzal Proterozoic granulites, Hoggar, Algeria)

The In Ouzzal granulitic unit (IOGU) consists predominantly of felsic orthogneisses most of which correspond to granitoids emplaced during the Archaean, plus metasediments, including olivine-spinel marbles, of late Archaean age. All units were metamorphosed at granulite facies during the Eburnean (2 Ga). The stable isotope signature of the marbles (δ¹³C=–0.8 to –4.2‰/PDB; δ¹⁸O = 7.9 to 18.9‰/SMOW) does not record a massive streaming of C-bearing fluids during metamorphism. Most of the isotopic variation in the marbles is explained in terms of pregranulitic features. Metasomatic transformation of granulites into layered potassic syenitic rocks and emplacement of carbonate veins and breccias occurred during retrogressive granulite facies conditions. The chemistry of these rocks is comparable with that of fenites and carbonatites with high contents of (L)REEs, Th, U, F, C, Ba and Sr but, with respect to these elements, a relative depletion in Nb, Ta, Hf, Zr and Ti. The isotopic compositions of Nd (?Nd_(T)=–6.3 to –9.9), of Sr (⁸⁷Sr/⁸⁶Sr_(T)= 0.7093–0.7104), and the O isotopic composition of metasomatic clinopyroxene (δ¹⁸O = 6.9 to 8‰), all indicate that the fluid had a strong crustal imprint. On the basis of the C isotope ratios (δ¹³C =–3.5 to –9.7‰), the fluid responsible for the crystallization of carbonates and metasomatic alteration is thought to be derived from the mantle, presumably through degassing of mantle-derived magmas at depth. Intense interaction with the crust during the upward flow of the fluid may explain its chemical and isotopic signatures. The zones of metasomatic alteration in the In Ouzzal granulites may be the deep-seated equivalents of the zones of channelled circulation of carbonated fluids described at shallower levels in the crust.     

The Eocene corundum-bearing rocks in the Gangdese arc,south Tibet:Implications for tectonic evolution of the Himalayan orogen

The genesis of Liangguo corundum deposit in the southern Gangdese magmatic arc, east-central Himalaya, remains unknown. The present study shows that the corundum-bearing rocks occur as lenses with variable sizes in the Eocene gabbro that intruded into marble. These corundum-bearing rocks have highly variable mineral assemblage and mode. The corundum-rich rocks are characterized by containing abundant corundum, and minor spinel, ilmenite and magnetite, whereas the corundum-poor and corundum-free rocks have variable contents of spinel, plagioclase, sillimanite, cordierite, ilmenite and magnetite. The host gabbro shows variable degrees of hydration and carbonization. The corundum grains are mostly black, and rarely blue, and have minor Fe O and TiO_2. The spinel is hercynite, with high Fe O and low Mg O contents. The corundum-bearing rocks have variable but high Al_2O_3, FeO and TiO_2, and low SiO_2 contents. Inherited magmatic and altered zircons of the corundum-bearing rocks have similar U e Pb ages(~47 Ma) to the magmatic zircons of the host gabbro, indicating corundum-bearing rock formation immediately after the gabbro intrusion. We considered that emplacement of gabbro induced the contact metamorphism of the country-rock marble and the formation of silica-poor fluid. The channeled infiltration of generated fluid in turn resulted in the hydrothermal metasomatism of the gabbro, which characterized by considerable loss of Si from the gabbro and strong residual enrichment of Al. The metasomatic alteration probably formed under Pe T conditions of ~2.2 -2.8 kbar and ~650 -700℃. We speculate that SiO_2, CaO and Na_2O were mobile, and Al_2O_3, FeO, TiO_2 and high field strength elements remained immobile during the metasomatic process of the gabbro. The Liangguo corundum deposit, together with metamorphic corundum deposits in Central and Southeast Asia, were related to the Cenozoic Himalayan orogeny, and therefore are plate tectonic indicators.     

Fluid composition and origin in the hydrothermal system of the Nezhdaninsky gold deposit,Sakha (Yakutia), Russia

Petrochemical characteristics of igneous, sedimentary, and metasomatic rocks; chemical and isotopic compositions of minerals and fluids; and PT parameters of mineral formation at the Nezhdaninsky deposit are reported. A model of hydrothermal system formation is developed on this basis. In addition to decreasing Ba/Rb and Li/Mg ratios in the course of the hydrothermal process, resulting in the formation of ore-bearing metasomatic rocks, increasing K/Ba and diminishing K/Cs ratios indicate the probable participation of magmatic fluid in the ore deposition. The agreement of the K/Rb and K/Ba ratios with the values typical of the main trend of igneous rocks (MT) implies that the K, Rb, and Ba contents were distributed in the ore-forming hydrothermal fluid according to the ratios in the source magmatic chamber. The K/Rb ratios in metasomatic rocks correspond to the MT and approach the pegmatitic-hydrothermal trend and the composition of orthomagmatic fluid of Mo-W greisen. Similar REE patterns of igneous and terrigenous rocks do not allow the REE source to be constrained unequivocally. The lithological control of lithophile element distribution testifies to the supply of host rock components to the hydrothermal system. All studied rocks and minerals are enriched in LREE. The REE total and the contribution of HREE decrease from preore to synore metasomatic rocks, from preore to regenerated carbonates, and from older to younger scheelite. A similar tendency is noted in granitoids of the Kurum pluton. The δ¹⁸O values of quartz range from +10.3 to +12.6‰ in Au-Mo-W zones, from +15.9 to +16.4‰ in metasomatic rocks, from +14.8 to +16.6‰ in gold-ore veins, and from +13.5 to +16.9‰ in silver-base-metal ore mineralization. The estimates of \(\delta ^{18} O_{H_2 O} \) suggest that water was supplied from a magmatic source (δ¹⁸O = +(5.5?9.0‰)) and as a product of sedimentary rock dehydration. High-temperature (up to 390°C) and highly concentrated (up to 31 wt % NaCl equiv) fluids participated in the mineral formation. The phase separation of the fluid into H₂O-CO₂ liquid and predominantly carbon dioxide gas was combined with mixing of a high-temperature and relatively highly concentrated chloride solution with a low-temperature and poorly mineralized fluid. The redox conditions varied from equilibrium with CH₄-bearing fluid at the gold-molybdenum-tungsten stage to equilibrium with CO₂-bearing fluid during the gold-ore stage.     

Geochemistry of phlogopite, diopside, calcite, anhydrite and apatite pegmatites and syenites of southern Madagascar: evidence for crustal silicocarbonatitic (CSC) melt formation in a Panafrican collisional tectonic setting

The phlogopite, diopside, calcite, anhydrite and apatite pegmatites of Ampandrandava and Beraketa are examples for the many other pegmatites of similar silicocarbonatitic composition found in the Bekily and Betroka-Beraketa Precambrian belts of southern Madagascar. The two studied pegmatites and associated syenites crystallised from immiscible silicocarbonatitic and peralkaline syenitic melts in a time span between 515 and 504 Ma in the final extensional phase of the Panafrican continental collision and connected metamorphic/metasomatic event. Model T _Nd ages suggest that the melts were produced by partial melting of 3.5 Ga partially evaporitic continental crust. The studied pegmatites and genetically associated syenitic rocks are very rare examples for crustal silicocarbonatitic melts generated in a Panafrican collisional setting. The overwhelming majority of carbonatites and associated peralkaline rocks are mantle derived, much poorer in phosphate and sulfate and found in a cratonic environment. In light of the present results, genetic models for other sulfate- and phosphate-rich magmatic rocks (e.g., phlogopite–apatite–calcite mineralisations in the Grenville-Hasting formation in Canada and in the Sludyanka group in Eastern Siberia) should be reevaluated.     

Hf-Pb isotope and trace element constraints on the origin of the Jacupiranga Complex (Brazil): Insights into carbonatite genesis and multi-stage metasomatism of the lithospheric mantle

The Lower Cretaceous Jacupiranga complex, in the central-southeastern portion of the South American Platform, includes carbonatites in close association with silicate rocks (i.e. strongly and mildly silica-undersaturated series). Here we document the first hafnium isotope data on the Jacupiranga complex, together with new trace element and Pb isotope compositions. Even though liquid immiscibility from a carbonated silicate melt has been proposed for the genesis of several Brazilian carbonatites, isotopic and geochemical (e.g., Ba/La ratios, lack of pronounced Zr-Hf and Nb-Ta decoupling) information argues against a petrogenetic relationship between Jacupiranga carbonatites and their associated silicate rocks. Thus, an origin by direct partial melting of the mantle is considered. The isotopic compositions of the investigated silicate samples are coherent with a heterogeneously enriched subcontinental lithospheric mantle (SCLM) source of rather complex evolution. At least two metasomatic processes are constrained: (1) a first enrichment event, presumably derived from slab-related fluids introduced into the SCLM during Neoproterozoic times, as indicated by consistently old T_DM ages and lamprophyre trace signatures, and (2) a Mesozoic carbonatite metasomatism episode of sub-lithospheric origin, as suggested by εNd-εHf values inside the width of the terrestrial array. The Jacupiranga parental magmas might thus derive by partial melting of distinct generations of metasomatic vein assemblages that were hybridized with garnet peridotite wall-rocks.     

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.     

Metasomatic transformations of carbonate rocks observable in quarries of Riverside, California, United States

The results of skarn-forming processes at contacts of the multiphase Southern California Batholith with carbonate rocks accessible to study in quarries in Riverside, California, involve prograde metasomatic transformations of marmorized dolomites and calcareous rocks in contact with granitic melts and contaminated magmas. The processes of contact assimilation are proved to have been controlled by the emplacement of granitic melts overheated relative to subliquidus melts (with the overheated melts prone to approach the composition of granodiorite, syenite, and gabbro) into skarnified marbles. The degree of magma overheating was evaluated based on G.F. Smith’s data on linear melting temperature variations for anhydrous intrusive rocks with various SiO₂ concentrations (<750°C for granites and >1100°C for contaminated rocks, ΔT 350°). This corresponds to the thermal regime of the development of mineralogically contrasting hypabyssal skarn aureoles: magnesian at contacts with granite magmas and calcic at contacts with melts of high basicity. The peripheral parts of the aureoles ubiquitously contain preserved zones of forsterite calciphyres and periclase marbles, whereas skarns at mafic intrusions consist of high-temperature silicates of decreasing Mg contents: monticellite, merwinite, melilite, and spurrite. Prograde and retrograde mineralforming processes in the metasomatic rocks and their facies affiliation are analyzed, and the chemical composition of the minerals are examined. The Riverside skarn aureoles are compared with other compositionally contrasting skarn aureoles that developed in contacts with granite magmas and melts of increasing basisity.