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The Vuoriyarvi Devonian carbonatite–ijolite–pyroxenite–olivinite complex comprises several carbonatite fields: Neske Vara, Tukhta-Vara, and Petyayan-Vara. The most common carbonatites in the Tukhta-Vara and Neske-Vara fields are calciocarbonatites, which host several P, Fe, Nb, and Ta deposits. This paper focuses on the Petyayan-Vara field, in which the primary magmatic carbonatites are magnesian. The least altered magnesiocarbonatites are composed of dolomite with burbankite and are rich in REE (up to 2.0 wt. %), Sr (up to 1.2 wt. %), and Ba (up to 0.8 wt. %). These carbonatites underwent several stages of metasomatism. Each metasomatic event produced a new rock type with specific mineralization. The introduction of K, Si, Al, Fe, Ti, and Nb by a F-rich fluid (or fluid-saturated melt) resulted in the formation of high-Ti magnesiocarbonatites and silicocarbonatites, composed of dolomite, microcline, Ti-rich phlogopite, and Fe–Ti oxides. Alteration by a phosphate–fluoride fluid caused the crystallization of apatite in the carbonatites. A sulfate-rich Ba–Sr–rare-earth elements (REE) fluid (probably brine-melt) promoted the massive precipitation of ancylite and baryte and, to a lesser extent, strontianite, bastnäsite, and synchysite. Varieties of carbonatite that contain the highest concentrations of REE are ancylite-dominant. The influence of sulfate-rich Ba-Sr-REE fluid on the apatite-bearing rocks resulted in the dissolution and reprecipitation of apatite in situ. The newly formed apatite generation is rich in HREE, Sr, and S. During late-stage transformations, breccias of magnesiocarbonatites with quartz-bastnäsite matrixes were formed. Simultaneously, strontianite, quartz, calcite, monazite, HREE-rich thorite, and Fe-hydroxides were deposited. Breccias with quartz-bastnäsite matrix are poorer in REE (up to 4.5 wt. % total REE) than the ancylite-dominant rocks (up to 11 wt. % total REE).

This article is devoted to the geology of titanium-rich varieties of the Petyayan-Vara rare-earth dolomitic carbonatites in Vuoriyarvi, Northwest Russia. Analogues of these varieties are present in many carbonatite complexes. The aim of this study was to investigate the behavior of high field strength elements during the late stages of carbonatite formation. We conducted a multilateral study of titanium-and niobium-bearing minerals, including a petrographic study, Raman spectroscopy, microprobe determination of chemical composition, and electron backscatter diffraction. Three TiO 2 -polymorphs (anatase, brookite and rutile) and three pyrochlore group members (hydroxycalcio-, fluorcalcio-, and kenoplumbopyrochlore) were found to coexist in the studied rocks. The formation of these minerals occurred in several stages. First, Nb-poor Ti-oxides were formed in the fluid-permeable zones. The overprinting of this assemblage by residual fluids led to the generation of Nb-rich brookite (the main niobium concentrator in the Petyayan-Vara) and minerals of the pyrochlore group. This process also caused niobium enrichment with of early generations of Ti oxides. Our results indicate abrupt changes in the physicochemical parameters at the late hydro (carbo) thermal stage of the carbonatite formation and high migration capacity of Ti and Nb under these conditions. The metasomatism was accompanied by the separation of these elements.

Abstract. Raman spectra of three natural carbonophosphates (sidorenkite, bonshtedtite, and bradleyite) with the general formula Na3MCO3PO4 (M is Mn, Fe, and Mg) were studied and compared. These spectra showed from 21 to 24 vibrational bands, of which the two most intense (964±5 and 1074±3 cm−1) correspond to the υ1(P–O) and υ1(C–O) modes. These two bands split into doublet peaks due to the occurrence of isomorphic impurities. It was found that the crystallographic orientation of the sample influences the intensity of most bands. Most bands assigned to the same vibrations showed a regular shift (the smallest in sidorenkite spectra, an intermediate in bonshtedtite, and the largest in bradleyite). We propose an algorithm that allows for diagnostics of carbonophosphates in inclusions by their Raman spectra, providing a reliable result even in the absence of energy-dispersive X-ray spectroscopy (EDX) data.

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<p>Along with some other Na-minerals, carbonophosphates indicate a high initial Na activity in carbonatite and kimberlite melts, which is beneficial for petrological reconstructions. Because carbonophosphates are capable of incorporating large-ion lithophile and rare earth elements (REEs) in their structure, they can participate in the transport of these elements. Moreover, due to the presence of both [PO<sub>4</sub>]<sup>3−</sup> and [CO<sub>3</sub>]<sup>2− </sup>groups in carbonophosphates, these mineral phases play an important role in the Earth's global carbon and phosphate cycles. With all these properties, carbonophosphates have long attracted the attention of geologists. Raman spectroscopy appears to be one of the most suitable tools for their diagnosis, since they commonly present in rocks as small inclusions in other mineral grains. Despite this profit, only a few publications contain Raman characteristics of either natural or synthetic carbonophosphates.</p><p>We studied and compared Raman spectra of three natural carbonophosphate phases (sidorenkite, bonshtedtite, and bradleyite) with the general formula Na<sub>3</sub>MCO<sub>3</sub>PO<sub>4</sub> (M = Mn, Fe, and Mg, correspondingly). These spectra showed from 21 to 24 vibrational bands, of which the two most intense (963±5 cm<sup>-1</sup> и 1074±3 cm<sup>-1</sup>) correspond to the ν1(P–O) and ν1(C–O) modes. These two bands split due to the occurrence of isomorphic impurities. It was found that the crystallographic orientation of the sample influences the intensity of most bands. A natural increase in the Raman shift was observed for most bands assigned to the same vibrations (the smallest shift in the spectrum is characteristic of sidorenkite, an intermediate - of bonshtedtite, and the largest - of bradleyite).</p><p>We propose the following algorithm for the diagnosis of carbonophosphates:</p><ul><li>Checking minerals for belonging to the group of carbonophosphates by the main bands and the characteristic profile of the spectrum;</li> <li>Testing the hypothesis that the mineral of question is bradleyite based on the analysis of the estimated shift of the main bands;</li> <li>Diagnosis of a mineral species by peaks located between the main bands;</li> <li>Validation of the diagnostics by considering the position of the bands at 185±9 cm<sup>-1</sup>, 208±7 cm<sup>-1</sup>, 255±5 cm<sup>-1</sup>, and 725±6 cm<sup>-1</sup>.</li> </ul><p>The proposed algorithm allows one to perform Raman diagnostics of carbonophosphates in inclusions even in the absence of EPMA data. In the study of carbonatites, kimberlites, and other rocks, the diagnostics of the mineral species of the carbonophosphate group can be important in the petrological aspect.</p><p>This research was funded by the Russian Science Foundation, grant number 19-77-10039.</p>

The Sallanlatva massif belongs to the group of Paleozoic alkaline-ultrabasic complexes wide spread in the Kola Region (the northwestern part of the Fennoscandian Shield). In the central part of this massif, the host ijolite and urtites contain calcite, ankerite, ankerite-dolomite and siderite carbonatites. The explosive processes that led to the formation of carbonatite breccias in the calcite and ankerite-dolomite carbonatites occurred in Sallanlatva massife in the last stages of the carbonatite magmatism. There are two types of explosive carbonatite breccias in the Sallanlatva massif: (1) glimmerite-calciocarbonatite breccias, and (2) siderite-dolomite breccias. Analysis of the mineral composition of fragments and matrix and the shape of fragments in breccias has shown that the first material to intrude into the host calcite and ankerite-dolomite carbonatites was calcite melt. After that, dolomite melt penetrated through the fracture zones, which resulted in the formation of siderite-dolomite breccias. The differences in the mineral composition of the breccia matrix suggest that the residual carbonatite melts originate from separate magma chambers. The chamber with calcite melt was located at great depth, and some captured glimmerite fragments were abraded during the melt upwelling. Silicate-dolomite melts lifted from a shallower depth; the captured fragments of siderite carbonatites retained their angular shape. Late hydrothermal processes yielded veins and caverns with Ba-Sr-P-S-Ti-REE mineralization in the breccias and host rocks.