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.     

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios (0.268–0.892) together with their respective Sr–Nd–Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle “hybridization”, metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5–25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re–Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu–Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.     

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 %.     

Ree minerals of alkaline metasomatic rocks in the Main Sayan Fault

The composition of accessory REE minerals (allanite, chevkinite, fergusonite, and REE carbonates) in alkaline metasomatic rocks of the Main Sayan Fault (quartz-albite-microcline-riebeckite-aegirine, quartzalbite-microcline-magnetite, and clinopyroxene-albite) was studied using back-scattered scanning electron microscopy. Chevkinite occurs only in quartz-albite-microline metasomatic rock. The paragenesis of allanite and titanite is stable in clinopyroxene-albite metasomatic rocks. Allanite and fergusonite are typical of all zones of the metasomatic column. Chevkinite and allanite are often altered due to interaction with hydrothermal fluid and lose some amount of LREE. Secondary bastnaesite, synchysite, and ancylite are formed after allanite, while secondary monazite is developed after chevkinite. Presumably, the low-temperature alteration of allanite and chevkinite under effect of F^?, CO ₃ ^2? , and P ₄ ^3? -bearing fluids had not any significant manifestation in the total REE content in metasomatic rocks.     

Leaching rare-earth and radioactive elements from alkaline rocks of the Lovozero Massif,Kola Peninsula

The paper presents data on the leaching efficiency of rare-earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) and radioactive (Th and U) elements by various reagents from alkaline rocks of the Lovozero Massif. Element concentrations were analyzed by ICP-MS and instrumental neutral activation (INAA). A new complex technique is suggested for analyzing elements on the solid phase of polymer hydrogels. This technique makes it possible to enhance the sensitivity and selectivity of INAA when these elements are simultaneously contained in rocks. Data are presented on the selective leaching of trace elements and the application of environmentally safe reagents.     

竹山下铀矿床碱交代岩特征与铀成矿关系

围岩与热液所发生的的置换作用称为交代作用,顾名思义碱交代作用就是钾、钠碱金属性化学物质参与交代作用。碱金属(钾、钠)带进热液蚀变岩称为碱交代岩。所以碱交代作用主要是以热液作用为主体,对金属元素成矿物质的迁移和富集成矿起到了很重要的作用。诠释了热液作用是成矿物质富集的驱动力。碱交代岩是竹山下铀矿床主要的蚀变类型之一。通过对竹山下碱交代型铀矿床的钻孔20-1碱交代岩进行野外踏勘采集样品、室内岩相学分析和电子探针成分分析研究,确定了竹山下地区碱交代作用对铀矿床的实质为钾交代作用,碱交代作用使得富铀岩石中的惰性铀成为活性铀,从而被活化迁移,富集成矿。     

The Lac Cornu retrograded eclogites (Aiguilles Rouges massif,Western Alps,France): evidence of crustal origin and metasomatic alteration

Metabasic rocks interbedded in amphibolite facies supracrustal gneisses outcrop around Lac Carnu in the Aiguilles Rouges massif (Western Alps). The cores of the thickest boudinaged lenses are made up of eclogitic amphibolites grading outwards into amphibolites. The common assemblage is unzoned garnet + symplectitic clinopyroxebe + hornblende + plagioclase. In a slightly amphibolitized sample, minimum P and T conditions of equilibrium between garnet and omphacite inclusions are 780°C and 11 Kb. A polymetamorphic pre-Alpine evolution of the massif is thus demonstrated. Eclogitic amphibolites show variations in major element composition similar to the Skaergaard evolution in the Al₂O₃ ? FeO + Fe₂O₃ ? MgO triangle. Variation diagrams in which Zr is taken as differentiation index also indicate magmatic trends for Mn, Ti, P, Ni, Co, Y, V and Cr, Ca, K, Na, Sr, Rb and Si were mobile during the evolution of the rocks. The igneous trend can be described by a quantitative model of fractional crystallization in which a noritic assemblage separated in the initial stage. This provides evidence of crustal P, T conditions of differentiation for the original materoal and in situ evolution for the eclogites. A second group of amphibolites shows banded structure and transitional terms with the surrounding gneisses. A volcano-sedimentary origin is suggested though the process cannot be modelled. The rocks may result from complex interactions of magnetic, metasomatic and sedimentary processes. It is concluded that Lac Cornu metabasites were originally continental tholeiites, though several geochemical criteria tend to indicate an oceanic origin. This casts some doubt on the validity of these criteria, when applied to metamorphic rocks.     

Geochemistry of silicic magmas in the Macolod Corridor, SW Luzon, Philippines: evidence of distinct, mantle-derived, crustal sources for silicic magmas

Silicic volcanic deposits (>65 wt% SiO₂), which occur as domes, lavas and pyroclastic deposits, are relatively abundant in the Macolod Corridor, SW Luzon, Philippines. At Makiling stratovolcano, silicic domes occur along the margins of the volcano and are chemically similar to the silicic lavas that comprise part of the volcano. Pyroclastic flows are associated with the Laguna de Bay Caldera and these are chemically distinct from the domes and lavas at Makiling stratovolcano. As a whole, samples from the Laguna de Bay Caldera contain lower concentrations of MgO and higher concentrations of Fe₂O_3(t) than the samples from domes and lavas. The Laguna de Bay samples are more enriched in incompatible trace elements. The silicic rocks from the domes, Makiling Volcano and Laguna de Bay Caldera all contain high alkalis and high K₂O/Na₂O ratios. Melting experiments of primitive basalts and andesites demonstrate that it is difficult to produce high K₂O/Na₂O silicic magmas by fractional crystallization or partial melting of a low K₂O/Na₂O source. However, recent melting experiments (Sisson et al., Contrib Mineral Petrol 148:635–661, 2005) demonstrate that extreme fractional crystallization or partial melting of K-rich basalts can produce these silicic magmas. Our model for the generation of the silicic magmas in the Macolod Corridor requires partial melting of mantle-derived, evolved, moderate to K-rich, crystallized calc-alkaline magmas that ponded and crystallized in the mid-crust. Major and trace element variations, along with oxygen isotopes and ages of the deposits, are consistent with this model. Electronic Supplementary Material Supplementary material is available for this article at     

Pyroxenes of the Khibiny alkaline pluton, Kola Peninsula

Seven pyroxene varieties were identified in nepheline syenites and foidolites of the Khibiny pluton: enstatite, ferrosilite, diopside, hedenbergite, augite, aegirine-augite, and aegirine. Enstatite and augite are typical of alkaline and ultramafic rocks of dike series. Ferrosilite was found in country quartzitic hornfels. Diopside is a rock-forming mineral in alkaline and ultramafic rocks, alkali gabbroids, hornfels in xenoliths of volcanic and sedimentary rocks and foyaite, melteigite-urtite that assimilate them, and certain hydrothermal pegmatite veins. Hedenbergite was noted in hornfels from xenoliths of volcanic and sedimentary rocks and in a hydrothermal pegmatite vein at Mount Eveslogchorr. Aegirine-augite is the predominant pyroxene in all types of nepheline syenites, phonolites and tinguaites, foidolites, alkaline and ultramafic rocks of dike series, fenitized wall rocks surrounding the pluton, and xenoliths of Devonian volcanic and sedimentary rocks. Aegirine is an abundant primary or, more often, secondary mineral in nepheline syenites, foidolites, and hydrothermal pegmatite veins. It occurs as separate crystals, outer zones of diopside and aegirine-augite crystals, and homoaxial pseudomorphs after Na-Ca amphiboles. Microprobe analyses of 265 pyroxenes samples allowed us to distinguish ten principal trends of isomorphic replacement and corresponding typomorphic features of pyroxenes. Compositional variations in clinopyroxenes along the sampled 35-km profile from the margin of the Khibiny pluton to its center confirm the symmetric zoning of the foyaite pluton relative to semicircular faults of the Minor Arc and the Main (Central) Ring marked by Devonian volcanic and sedimentary rocks, foidolites, and related metasomatic rocks (rischorrite, albitite, and aegirinite). Changes in the composition of pyroxenes are explained mainly by the redistribution of elements between coexisting minerals of foyaites in the process of their intense differentiation under the effect of foidolite melts that have intruded into the circular fault zones.     

Variation of chemical composition of alkaline granitic rocks in the central part of the Kola Peninsula

Chemical composition and origin of alkaline granitic rocks in the Keivy area on the Kola Peninsula were investigated. Linear correlation analysis and principal-component analysis were used to determine the interrelation of major petrogenetic elements in alkaline granite and surrounding alkaline metasomatites. Estimates of linear correlation coefficients turned out to be different, and principal-component analysis of the chemical data revealed that there were three main components influencing variation of chemical composition. These factors can be interpreted in terms of petrological processes, which are different for alkaline granite and for the surrounding metasomatites, indicating a different origin of the rocks.     

Two-stage contamination during crustal assimilation: isotopic evidence from volcanic rocks in eastern Nevada

Thousands of cubic kilometers of dominantly intermediate composition, metaluminous magma erupted at approximately 35 Ma in eastern Nevada. Two stages of crustal contamination are inferred from detailed study of the earliest vocanic rocks. Fine-grained mafic rocks and rocks with mixed textures, ranging from basalt to rhyolite, were contaminated with a crustal component rich in Nd but poor in Sr. Overlying plagioclaserich andesites and dacites have greater Sr and ⁸⁷Sr/⁸⁶Sr, but less Nd and lower _Nd and are interpreted to have been contaminated by a crustal component with the opposite elemental signature (i.e., poor in Nd but rich in Sr). The first contaminant represents a partial melt of the crust with plagioclase as a residual phase and the second contaminant is the residue of the partial melting event, or bulk crust. The net effect is bulk crustal assimilation, but in two bites. The separation of the crustal souree into two elementally distinct contaminants causes divergent trends with respect to the variation of ⁸⁷Sr/ ⁸⁶Sr versus _Nd that could be misinterpreted to indicate the existence of isotopically distinct crustal reservoirs. Comparison of the calculated contaminants to melting relationships in pelites is consistent with the two contammants representing melt and residue at about 30% melting. The model age of the bulk crust is approximately 2.2 Ga, consistent with an early Proterozoic crustal province inferred by other workers.     

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.     

Rb-Sr and U-Th-Pb systematics of alkaline rocks: the alkaline rocks from Italy

The isotopic composition of Pb and Sr and the abundances of Rb, Sr, U, Th, and Pb were determined for whole rock samples from all major volcanic centres of the Cenozoic alkaline volcanism of Central and South Italy, together with some samples from the contemporaneous anatectic Tuscan volcanism. The Sr and Pb isotopic compositions of the alkaline rocks show a negative correlation combined with a regional trend: the ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios decrease from 0.711 in the north-west to 0.704 in the south-east, while the ${}^{206}\text{Pb}{}^{204}\text{Pb}$ ratios increase from 18.7 to 20.0. Variations in both isotopic compositions are generally small throughout erupted rock sequences for any volcanic centre.The Pb and Sr isotopic abundance variations are interpreted on the basis of two alternative models, which correspond to two groups of geological processes: variations can result (i) from a time dependent development in subsystems with different $\text{Rb}\text{Sr}$ or $\text{U(Th)}\text{Pb}$ ratios or, (ii) from mixing of Sr or Pb with different isotopic compositions. Combining both Pb and Sr isotope abundance measurements it is shown that the source of each volcanic centre is formed by various degrees of mixing between two components. One component and the most southern Tuscan anatectic rocks most likely have a common source, whereas the other component of the mixing process is suggested to be a liquid fraction derived from a small degree of partial fusion of a hydrous mantle. Thus at least a two-stage evolution of the Italian alkaline rocks is indicated: first a mixing process leading to the formation of the parental material followed by differentiation processes leading to the formation of the erupted rock sequences.The geodynamic model which explains the data best is that of a lateral inhomogeneous mantle. The lateral inhomogeneities in the mantle would be the result of mixing between originally mantle and crustal derived material. The mixing process itself would not have any primary connection with the Quarternary volcanic activity.     

Role of fluid in the genesis of carbonatites and alkaline rocks: Geochemical evidence

In most alkaline-ultrabasic-carbonatite ring complexes, the distribution of trace elements in the successive derivatives of mantle magmas is usually controlled by the Rayleigh equation of fractional crystallization in accordance with their partition coefficients, whereas, that of late derivatives, nepheline syenites and carbonatites, is usually consistent with trends characteristic of silicate-carbonate liquid immiscibility. In contrast to the carbonatites of ring complexes, carbonatites from deep-seated linear zones have no genetic relation with alkaline-ultrabasic magmatism, and the associated alkaline rocks are represented only by the nepheline syenite eutectic association. The geochemical study of magmatic rocks from the Vishnevye Gory nepheline syenite-carbonatite complex (Urals), which is assigned to the association of deep-seated linear zones, showed that neither differentiation of a parental melt nor liquid immiscibility could produce the observed trace element distribution (Sr, Rb, REE, and Nb) in miaskites and carbonatites. Judging from the available fragmentary experimental data, the distribution patterns can be regarded as possible indicators of element fractionation between alkaline carbonate fluid and alkaline melt. Such trace element distribution is presumably controlled by a fluid-melt interaction; it was also observed in carbonatites and alkaline rocks of some ring complexes, and its scarcity can be explained by the lower density of aqueous fluid released from magma at shallower depths.     

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.