Amphiboles of the Khibiny alkaline pluton, Kola Peninsula, Russia

The rocks of the Khibiny pluton contain 25 amphibole varieties, including edenite, fluoredenite, kaersutite, pargasite, ferropargasite, hastingsite, magnesiohastingsite, katophorite, ferrikatophorite, magnesiokatophorite, magnesioferrikatophorite, magnesioferrifluorkatophorite, ferrimagnesiotaramite, ferrorichterite, potassium ferrorichterite, richterite, potassium richterite, potassium fluorrichterite, arfvedsonite, potassium arfvedsonite, magnesioarfvedsonite, magnesioriebeckite, ferriferronyboite, ferrinyboite, and ferroeckermannite. The composition of rock-forming amphiboles changes symmetrically relative to the Central Ring of the pluton; i.e., amphiboles enriched in K, Ca, Mg, and Si are typical of foyaite near and within the Central Ring. The Fe and Mn contents in amphiboles increase in the direction from marginal part of the pluton to its center. Foyaite of the marginal zone contains ferroeckermannite, richterite, arfvedsonite, and ferrorichterite; edenite is typical of foyaite and hornfels of the Minor Arc. Between the Minor Arc and the Central Ring, foyaite contains ferroeckermannite, arfvedsonite, and richterite; amphiboles in rischorrite, foidolite and hornfels of the Central Ring are (potassium) arfvedsonite, (potassium) richterite, magnesiokatophorite, magnesioarfvedsonite, ferroeckermannite, and ferriferronyboite; amphiboles in foyaite within the Central Ring, in the central part of the pluton, are arfvedsonite, magnesioarfvedsonite, ferriferronyboite, katophorite, and richterite. It is suggested that such zoning formed due to the alteration of foyaite by a foidolite melt intruded into the Main (Central) Ring Fault.     

Rock-Forming feldspars of the Khibiny alkaline pluton,Kola Peninsula,Russia

This paper describes the structural-compositional zoning of the well-known Khibiny pluton in regard to rock-forming feldspars. The content of K-Na-feldspars increases inward and outward from the Main foidolite ring. The degree of coorientation of tabular K-Na-feldspar crystals sharply increases in the Main ring zone, and microcline-dominant foyaite turns into orthoclase-dominant foyaite. The composition of K-Na-feldspars in the center of the pluton and the Main ring zone is characterized by an enrichment in Al. This shift is compensated by a substitution of some K and Na with Ba (the Main ring zone) or by an addition of K and Na cations to the initially cation-deficient microcline (the central part of the pluton). Feldspars of volcanosedimentary rocks occurring as xenoliths in foyaite primarily corresponded to plagioclase An_15–40, but high-temperature fenitization and formation of hornfels in the Main ring zone gave rise to the crystallization of anorthoclase subsequently transformed into orthoclase and albite due to cooling and further fenitization. Such a zoning is the result of filling the Main ring fault zone within the homogeneous foyaite pluton with a foidolite melt, which provided the heating and potassium metasomatism of foyaite and xenoliths of volcanosedimentary rocks therein. The process eventually led to the transformation of foyaite into rischorrite-lyavochorrite, while xenoliths were transformed into aluminum hornfels with anorthoclase, annite, andalusite, topaz, and sekaninaite.     

Corundum-group minerals in rocks of the Khibiny alkaline pluton,Kola Peninsula

Five minerals of the corundum group have been identified in the Khibiny pluton with certainty. Corundum proper and karelianite occur only in hornfels after volcanic and sedimentary rocks. Xenoliths of hornfels mark the ring faults that bound foidalite within the field of foyaite. Hematite occurs in hydrothermally altered nepheline syenite and crosscutting hydrothermal veins related to the ring faults. Minerals of the ilmenite-pyrophanite series are present in all rocks of the pluton, including veins. Accessory ilmenite in foyaite varies from the manganese variety and pyrophanite in the inner and outer parts of the pluton to manganese-free ilmenite in zone of the Main Ring Fault. In xenoliths of volcanic rocks and alkaline ultramafic rocks, ilmenite is enriched in magnesium. The zoning in distribution of the above-mentioned minerals and the character of variation in their compositions from margins of the pluton to its center are consistent with the petrochemical zoning formed as a result of foyaite alteration of near ring faults.     

Spinel-group minerals in rocks of the Khibiny alkaline pluton,Kola Peninsula

Seven spinel-group minerals in various geological settings have been revealed in the rocks of the Khibiny pluton. Hercynite, gahnite, and vuorelainenite occur only in xenoliths of hornfels after volcanic and sedimentary rocks, whereas spinel and magnesiochromite occur in alkaline ultramafic rocks of dike series. Franklinite has been discovered in a low-temperature hydrothermal vein. Ubiquitous magnetite is abundant in foyaite, foidolites, alkaline ultrabasic rocks, and pegmatite and hydrothermal veins and may even be the main mineral in some foidolite varieties. The spinel-group minerals are characterized by various chemical compositions due to the fractionation of nepheline syenites resulting in formation of the Main ring of foidolites and apatite-nepheline ore. Like most other minerals found throughout the pluton, magnetite is characterized by variation in the chemical composition along the radial line from the contact with country Proterozoic volcanic rocks to the geometric center of the pluton. Toward the center, the total Ti and Mn contents in magnetite increase from 5–15 up to 40 at %.     

Kalsilite of the Khibiny and Lovozero alkaline plutons,Kola Peninsula

Kalsilite—a typical mineral of ore-bearing zones of the Khibiny and Lovozero plutons—was formed after low-Si and high-K nepheline in one of three ways: (1) by relatively high-temperature replacement of Na with K; (2) due to orthoclase-kalsilite poikiloblastesis in foidolites and overlapping foyaites; or (3) by replacement of nepheline with zeolite.     

Relationship between oxosilicate niobium mineralization and organic matter in alkaline pegmatites of the Khibiny pluton,Kola Peninsula

In alkaline pegmatites of the Khibiny pluton niobium oxosilicates with (Nb + Ti)/Si ≥ 1 and Nb > Ti occur in intimate fine intergrowths with endogenic organic matter, which makes it possible to assume a genetic relationship between them. Such intergrowths from pegmatites of Mounts Kukisvumchorr and Koashva have been studied by electron microscopy, electron microprobe, IR spectroscopy, and exclusion chromatography. Unsaturated hydrocarbon groups, including aromatic ones, and carboxylate groups are prevalent in the organic matter intergrown with the niobium oxosilicates. The molecular weight distribution in the part of the bitumen soluble in tetrahydrofurane is polymodal, probably due to its formation as a result of parallel reactions on several catalytic centers of polymerization.     

Chromium mineralization in the Khibiny alkaline massif (Kola Peninsula,Russia)

This paper presents new data on chromium mineralization in a fenitized xenolith in Mt. Kaskasnyunchorr in the Khibiny alkaline massif (Kola Peninsula, Russia) and summarizes data on Cr mineralogy in the Khibiny Mountains. Protolith silicates that contained Cr³⁺ admixture are believed to be the source of this element in the fenite. Cr-bearing (maximum Cr₂O₃ concentrations, wt %, are in parentheses) aegirine (5.8), crichtonite-group minerals (2.1), muscovite (1.3), zirconolite (1.1), titanite (1.0), fluorine-magnesioarfvedsonite (0.8), biotite (0.8), ilmenite (0.6), and aenigmatite (0.6) occur in the fenite. The late-stage spinellides of the FeTi-chromite-CrTi-magnetite series, which are very poor in Mg and Al and which formed after Crrich aegirine and ilmenite, are the richest in Cr (up to 42% Ct₂O₃). Cr concentrations grew with time during the fenitization process. Unlike minerals in the Khibiny ultramafic rocks where Cr is associated with Mg, Al (it is isomorphic with Cr), and with Ca, chromium in the fenites is associated with Fe, Ti, and V (with which Cr³⁺ is isomorphic) and with Na in silicate minerals. Cr³⁺ Mobility of Cr³⁺ and the unique character of chromium mineralization in the examined fenites were caused by high alkalinity of the fluid.     

Elpasolite from hyperalkaline pegmatite of the Khibiny pluton, Kola Peninsula. Symmetry of elpasolite

Elpasolite, K₂NaAlF₆, has been found for the first time in a pegmatite related to peralkaline foid syenite at Mt. Koashva, Khibiny alkaline pluton, Kola Peninsula, Russia, as pale pink octahedral crystals up to 2 mm in size within cavities in the natrolite core of pegmatite in association with amicite, sodalite, aegirine, pectolite, catapleiite, sitinakite, lemmleinite-K, and vinogradovite. The chemical composition determined with an electron microprobe is as follows, wt %: 31.53 K; 9.22 Na; 11.20 Al; 47.21 F; total is 99.16. The empirical formula is K_1.96Na_0.98Al_1.01F_6.05. The infrared spectrum is given. The crystal structure has been refined to R = 0.030, space group Fm $ \bar 3 Elpasolite, K₂NaAlF₆, has been found for the first time in a pegmatite related to peralkaline foid syenite at Mt. Koashva, Khibiny alkaline pluton, Kola Peninsula, Russia, as pale pink octahedral crystals up to 2 mm in size within cavities in the natrolite core of pegmatite in association with amicite, sodalite, aegirine, pectolite, catapleiite, sitinakite, lemmleinite-K, and vinogradovite. The chemical composition determined with an electron microprobe is as follows, wt %: 31.53 K; 9.22 Na; 11.20 Al; 47.21 F; total is 99.16. The empirical formula is K_1.96Na_0.98Al_1.01F_6.05. The infrared spectrum is given. The crystal structure has been refined to R = 0.030, space group Fm m, a = 8.092 ?. The result of a special X-ray powder diffraction study confirmed the suggestion made by Morss (1974) that reflections violating space group Fm m in some published X-ray powder patterns of natural elpasolite are Kβ-lines. Original Russian Text ? I.V. Pekov, N.V. Chukanov, N.N. Kononkova, N.V. Zubkova, M.Kh. Rabadanov, D.Yu. Pushcharovsky, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, No. 6, pp. 76–84.     

Typochemistry of rinkite and products of its alteration in the Khibiny Alkaline pluton,Kola Peninsula

The occurrence, morphology, and composition of rinkite are considered against the background of zoning in the Khibiny pluton. Accessory rinkite is mostly characteristic of foyaite in the outer part of pluton, occurs somewhat less frequently in foyaite and rischorrite in the central part of pluton, even more sparsely in foidolites and apatite–nepheline rocks, and sporadically in fenitized xenoliths of the Lovozero Formation. The largest, up to economic, accumulations of rinkite are related to the pegmatite and hydrothermal veins, which occur in nepheline syenite on both sides of the Main foidolite ring. The composition of rinkite varies throughout the pluton. The Ca, Na, and F contents in accessory rinkite and amorphous products of its alteration progressively increase from foyaite and fenitized basalt of the Lovozero Formation to foidolite, rischorrite, apatite–nepheline rocks, and pegmatite–hydrothermal veins.     

Loparite-(Ce) from the Khibiny Alkaline Pluton,Kola Peninsula,Russia

Data on the occurrence, morphology, anatomy, composition, and formation conditions of loparite-(Ce) in the Khibiny alkaline pluton are given. Loparite-(Ce), (Na,Ce,Sr)(Ce,Th)(Ti,Nb)2O6, resulted from metasomatic alteration and assimilation of metamorphic host rocks at the contact with foyaite as well as foyaite on the contact with foidolite. This alteration was the highest in pegmatite, and albitite developed there. A decrease in temperature resulted in enrichment of the perovskite and tausonite endmembers in loparite-(Ce) owing to a decrease in the loparite and lueshite endmembers. La and Ce sharply predominate among rare earth elements in the composition of loparite-(Ce).     

Kyanoxalite,a new cancrinite-group mineral species with extraframework oxalate anion from the Lovozero alkaline pluton,Kola Peninsula

Kyanoxalite, a new member of the cancrinite group, has been identified in hydrothermally altered hyperalkaline rocks and pegmatites of the Lovozero alkaline pluton, Kola Peninsula, Russia. It was found at Mount Karnasurt (holotype) in association with nepheline, aegirine, sodalite, nosean, albite, lomonosovite, murmanite, fluorapatite, loparite, and natrolite and at Mt. Alluaiv. Kyanoxalite is transparent, ranging in color from bright light blue, greenish light blue and grayish light blue to colorless. The new mineral is brittle, with a perfect cleavage parallel to (100). Mohs hardness is 5–5.5. The measured and calculated densitiesare 2.30(1) and 2.327 g/cm³, respectively. Kyanoxalite is uniaxial, negative, ω = 1.794(1), ɛ = 1.491(1). It is pleochroic from colorless along E to light blue along O. The IR spectrum indicates the presence of oxalate anions C₂O₄²⁻ and water molecules in the absence of CO₃²⁻ Oxalate ions are confirmed by anion chromatography. The chemical composition (electron microprobe; water was determined by a modified Penfield method and carbon was determined by selective sorption from annealing products) is as follows, wt %: 19.70 Na₂O, 1.92 K₂O, 0.17 CaO, 27.41 Al₂O₃, 38.68 SiO₂, 0.64 P₂O₅, 1.05 SO₃, 3.23 C₂O₃, 8.42 H₂O; the total is 101.18. The empirical formula (Z = 1) is (Na_6.45K_0.41Ca_0.03)_Σ6.89(Si_6.53Al_5.46O₂₄)[(C₂O₄)_0.455(SO₄)_0.13(PO₄)_0.09(OH)_0.01]_Σ0.68 · 4.74H₂O. The idealized formula is Na₇(Al₅₋₆Si₆₋₇O₂₄)(C₂O₄)_0.5−1 · 5H₂O. Kyanoxalite is hexagonal, the space group is P6₃, a = 12.744(8), c = 5.213(6) -ray powder diffraction pattern are as follows, [d, [A] (I, %)(hkl)]: 6.39(44) (110), 4.73 (92) (101), 3.679 (72) (300), 3.264 (100) (211, 121), 2.760 (29) (400), 2.618 (36) (002), 2.216, (29) (302, 330). According to the X-ray single crystal study (R = 0.033), two independent C₂O₄ groups statistically occupy the sites on the axis 6₃. The new mineral is the first natural silicate with an additional organic anion and is the most hydrated member of the cancrinite group. Its name reflects the color (κɛανgoΣς is light blue in Greek) and the species-forming role of oxalate anions. The holotype is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration no. 3735/1.     

Low-sulfide PGE ore in the Volchetundra gabbro-anorthosite pluton, Kola Peninsula, Russia

The internal structure of the Volchetundra gabbro-anorthosite massif is considered, including localization of low-sulfide PGE mineralization and its mineralogy. The Volchetundra massif 24 km long and 0.5–4.0 km wide occupies the middle part of the Main Range complex, which extends for 75 km in the nearly meridional direction. The main and marginal zones are distinguished in the massif. The marginal zone 20–400 m wide extends along the entire eastern contact of the massif and is primarily composed of mediumgrained meso- and leucocratic norite, gabbronorite, plagioclasite, and less fequent orthopyroxenite. The main zone consists of coarse-grained leucogabbro and gabbronorite with an anorthosite zone in the axial part of the massif. The PGE mineralization of the Volchetundra massif is distinctly subdivided into two types substantially differing in localization, mineralogy, geochemistry, and economic importance. Mineralization of the first type is localized in the marginal zone and characterized by the highest resource potential. Mineralization hosted in the main zone belongs to the second type. The PGE ore of marginal zone is spatially and genetically related to the pyrite-pentlandite-chalcopyrite-pyrrhotite sulfide mineralization (1–5%) in the form of fine inequigranular interstitial disseminations, and less frequent larger grains and pockets localized within two ore zones each up to 2 km in extent. The thickness of separate mineralized layers varies from 0.5 to 3.0 m and up to 45 m in bulges. The average Pt + Pd grade is 1.37 gpt at Pd/Pt = 3.1. The mineralization of the second type has been penetrated by boreholes. Separate intersections do not correlate with one another and are limited in extent both along the strike and down the dip. The PGE mineralization is related to finely dispersed pentlandite-pyrite-pyrrhotite-chalcopyrite sulfides, sulfide emulsions, and less abundant stringer-disseminated sulfide ore. The orebodies vary from 2 to 7 m in thickness. The average Pt + Pd grade is 1.61 gpt; Pd/Pt = 1.3. The PGE mineralization includes 22 mineral species. PGE sulfides (cooperite-braggite-vysotskite; laurite and erlichmanite in insignificant amounts) are predominant. Bismuthotellurides (moncheite-kotulskite-merenskyite) and arsenides (sperrylite, palladoarsenite, arsenopalladinite, atheneite) are subordinate in abundance. In addition, sulfoarsenides (platarsite, hollingworthite), tellurides (telargpalite, sopcheite, keithconnite, melonite, hessite), paolovite, and Pt-Fe alloy have been identified. An admixture of native gold and electrum occur constantly.     

Thorium mineralization in hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton,Kola Peninsula

The Lovozero pluton (Kola Peninsula, Russia) is an unique object from the standpoint of the abundance, diversity, and originality of Th mineralization. In contrast to other igneous rocks and to such chemical elements as Ca, REE, U, and Na, Th in the hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton commonly occurs as its own mineral phases. Umbozerite Na₃Sr₄Th(Mn,Zn,Fe,Mg)[Si₈O₂₄](OH) (7 samples), Ti-Th silicate Na_0–7Sr_0–1ThTi_1–2Si₈O_22–23(OH) · nH₂O (8 samples), Na-Th silicate (Na,K)₄Th₃[Si₈(O,OH)₂₄] · nH₂O (6 samples), thorite (2 samples), steenstrupine-(Ce)-thorosteenstrupine series minerals (5 samples), and Th phosphate (Th,Na,K,Ca,Mg,U,Sr,Ba)[(P,Si, Al)₁O₄] · nH₂O (1 sample) were investigated in this study. Ti-Th silicates and Th phosphate have been described for the first time. All of the above-mentioned minerals have been examined with electron microprobe, IR spectroscopy, powder diffraction, thermogravimetric and optical methods. High-Th minerals such as steenstrupine, umbozerite, Th phosphate, and Na-Th silicates crystallized mainly during the ussingite stage of the pegmatite-forming process. At the early hydrothermal high-alkaline stage, steenstrupine was replaced with REE and Th aggregates (belovite, vitusite, seidite, Na-Th silicates, Ti-Th silicates, etc.). Thorite, Ti-Th silicates, and minerals of the rhabdophane and monazite groups were formed at the late hydrothermal low-alkaline stage. Despite the metamict features of almost all samples, stoichiometric ratios of cations in umbozerites and Ti-Th silicates remain stable. Clear relationships have been revealed between umbozerites and Ti-Th silicates, on the one hand, and seidite-(Ce), a Ti-silicate that has a zeolite-like structure, on the other. This implies that, under certain conditions, these minerals may be regarded as potential suppliers of Th to the environment due to the leaching of Th from zeolite channels.     

Behoite and mimetite from the Saharjok alkaline intrusion,Kola Peninsula

The detailed study of the mineral composition of the nepheline syenite pegmatite from the Saharjok Intrusion has resulted in the finding of behoite and mimetite, a mineral species identified in the Kola region for the first time. The pegmatite body at the contact between nepheline syenite and essexite is unusual in textural and structural features and combination of mineral assemblages including unique beryllium mineralization. Behoite Be(OH)₂ is an extremely rare beryllium mineral. It occurs as powderlike aggregates in the leaching cavities between euhedral pyroxene crystals. Behoite was identified by comparison of X-ray powder diffraction data of the studied mineral phase and behoite from the Be-bearing tuff in the type locality of this mineral (Utah, United States). Mimetite was found in the same pegmatite of the Saharjok intrusion. It forms unusual parallel-fibrous aggregates with individual fibers as long as ∼1 mm and only ∼1 μm across. X-ray powder diffraction data and the chemical composition characterize the mineral as hexagonal phase Pb₅[AsO₄]₃Cl. Both behoite and mimetite are the products of late hydrothermal alteration of primary minerals (meliphanite, galena, arsenopyrite, and loellingite). The secondary phases freely crystallized in the cavities remaining after the leached nepheline.     

On the problem of the formation and geochemical role of bituminous matter in pegmatites of the Khibiny and Lovozero alkaline massifs, Kola Peninsula, Russia

Solid bituminous matter (SBM) typically occurs in the late hydrothermal assemblages of pegmatites of the Khibiny and Lovozero massifs, being confined to a microporous framework Ti-, Nb-, and Zr-silicates, which are sorbents of small molecules and efficient catalysts of the polymerization, reforming, and selective oxidation of organic matter. Bituminous matter from the pegmatites of the Lovozero Massif typically have elevated contents of aliphatic hydrocarbons, sulfur, and sodium, but are depleted in oxygen and trace elements. SBM from the pegmatites of the Khibiny Massif are depleted in sulfur and enriched in oxygen-bearing derivatives of polycyclic aromatic hydrocarbons. Being complexing agents for Th, REE, Ba, Sr, and Ca, they play a key role in the transfer and accumulation of Th and in the accumulation of alkali earth and rare earth elements during the hydrothermal stage of mineral formation. Oxidized SBM bearing rare and alkali earth elements are complex microheterogenous systems, which contain mineral (Th silicates, calcite, etc.), metalorganic (with REE, Ca, Sr, Ba), and predominantly organic phases formed by the exsolution of initial metalorganic material with decreasing temperature.     

A reassessment of models for hydrocarbon generation in the Khibiny nepheline syenite complex, Kola Peninsula, Russia

Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H₂ which reacts with magmatically derived CO₂ to form CH₄ and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH₄ with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO₂-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450–550 °C at 2.8–4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. δ¹³C values for methane range from − 22.4‰ to − 5.4‰, confirming a largely abiogenic origin for the gas. The presence of primary CH₄-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in δ¹³C isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks.     

Possible mechanism of horizontal overpressure generation of the Khibiny,Lovozero, and Kovdor ore clusters on the Kola Peninsula

The paper discusses questions related to the generation of increasing crustal horizontal compressive stresses compared to the idea of the standard gravitational state at the elastic stage or even from the prevalence of horizontal compression over vertical stress equal to the lithostatic pressure. We consider a variant of superfluous horizontal compression related to internal lithospheric processes occurrin in the crust of orogens, shields, and plates. The vertical ascending movements caused by these motions at the sole of the crust or the lithosphere pertain to these and the concomitant exogenic processes giving rise to denudation and, in particular, to erosion of the surfaces of forming rises. The residual stresses of the gravitational stressed state at the upper crust of the Kola Peninsula have been estimated for the first time. These calculations are based on the volume of sediments that have been deposited in Arctic seas beginning from the Mesozoic. The data speak to the possible level of residual horizontal compressive stresses up to 90 MPa in near-surface crustal units. This estimate is consistent with the results of in situ measurements that have been carried out at the Mining Institute of the Kola Science Center, Russian Academy of Sciences (RAS), for over 40 years. It is possible to forecast the horizontal stress gradient based on depth using our concept on the genesis of horizontal overpressure, and this forecasting is important for studying the formation of endogenic deposits.