This work is the first in situ U–Pb geochronological study of perovskite and calcic garnet (andradite) from the Guli complex in the Maimecha–Kotuy alkaline province (Polar Siberia, Russia). The U–Pb isotopic compositions of perovskite from contact zones of the two carbonatite stocks (Southern and Northern) and from jacupirangite separating the stocks were determined by laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICPMS) and isotope-dilution thermal-ionisation mass-spectrometry (ID-TIMS). The LA-ICPMS and ID-TIMS data for perovskite from the Northern carbonatite stock are in good agreement, yielding 206Pb/238U ages of 250.4 ± 1.1 Ma and 249 ± 2 Ma, respectively. These ages are also within the analytical uncertainty from the ID-TIMS results for perovskite from jacupirangites (250 ± 1 Ma). The LA-ICPMS results for perovskite from the Southern carbonatite stock indicate its somewhat older age (255.3 ± 2.4 Ma), implying the possibility of small-volume mantle magmatism predating the eruption of the Siberian flood basalts at ca. 252–251 Ma. This interpretation is supported by reports of pre-flood magmatism elsewhere in eastern Siberia. Andradite crystals from the contact between the Southern stock and metasomatised melilitolite were analysed by ID-TIMS. These measurements are inconclusive (247 ± 6 Ma) and could not be used to constrain further the timing of carbonatitic magmatism in the southern part of the complex. The present contribution also presents a refined methodology for LA-ICPMS geochronological studies of perovskite with elevated levels of common lead, and addresses some of the problems with previously proposed calibration standards.

A major debris flow, the Trig Point Hill flow, originating from Kerimasi volcano (Tanzania) contains numerous blocks of extrusive/pyroclastic carbonatites similar to those exposed at the rim of the currently inactive crater. The blocks of calcite carbonatite consist of: (1) large clasts of corroded and altered coarse grained calcite; (2) primary prismatic inclusion bearing phenocrystal calcite; and (3) a matrix consisting primarily of fine-grained prismatic calcite. The large clasts are inclusion free and exhibit a ‘corduroy-like’ texture resulting from solution along cleavage planes. The resulting voids are filled by brown Fe–Mn hydroxides/oxides and secondary calcite. The prismatic or lath-shaped phenocrystal calcite is not altered and contains melt inclusions consisting principally of primary Na–Ca carbonates which contain earlier-formed crystals of monticellite, periclase, apatite, Mn–Mg-magnetite, Mn–Fe-sphalerite and Nb-perovskite. Individual Na–Ca carbonate inclusions are of uniform composition, and the overall range of all inclusions analysed (wt.%) is from 28.7 to 35.9 CaO; 16.7–23.6 Na2O; 0.5–2.8 K2O, with minor SO3 (1.1–2.2) and SrO (0.34–1.0). The Na–Ca carbonate compositions are similar to that of shortite, although this phase is not present. The Na–Ca carbonates are considered to be primary deuteric phases and not secondary minerals formed after nyerereite. Monticellite shows limited compositional variation and contains 2–4 wt.% MnO and 12 wt.% FeO and is Mn-poor relative to monticellite in Oldoinyo Lengai natrocarbonatite. Periclase is Fe-bearing with up to 13 wt.% FeO. Spinels are Cr-free, Mn-poor and belong to the magnetite–magnesioferrite series in contrast to Mn-rich spinels of the magnetite–jacobsite series occurring in Oldoinyo Lengai natrocarbonatite. The matrix in which the ‘corduroy’ clasts and phenocrystal calcite are set consists of closely packed small prisms of calcite lacking melt inclusions, with interstitial fine-grained apatite, baryte, strontianite and minor fluorite. Pore spaces are filled with secondary Mn–Fe hydroxides/oxides, anhydrite and gypsum. The hypothesis that flow-aligned calcite in volcanic calciocarbonatites from Kerimasi, Tinderet, Homa and Catanda is altered nyerereite is discussed and it is considered that these calcite are either primary phases or altered melilite. The nyerereite alteration hypothesis is discussed with respect to the volumetric and compositional aspects of pseudomorphism by dissolution–precipitation replacement mechanisms. This study concludes that none of the volcanic calciocarbonatites containing flow-aligned calcite phenocrysts are altered natrocarbonatite.

The Neoproterozoic Lofdal alkaline carbonatite complex consists of a swarm of carbonatite dykes and two plugs of calcite carbonatite known as the ‘Main’ and ‘Emanya’ carbonatite intrusions, with associated dykes and plugs of phonolite, syenite, rare gabbro, anorthosite and quartz-feldspar porphyry. In the unaltered Main Intrusion calcite carbonatite the principal rare-earth host is burbankite. As burbankite typically forms in a magmatic environment, close to the carbohydrothermal transition, this has considerable petrogenetic significance. Compositional and textural features of Lofdal calcite carbonatites indicate that burbankite formed syngenetically with the host calcite at the magmatic stage of carbonatite evolution. The early crystallisation of burbankite provides evidence that the carbonatitic magma was enriched in Na, Sr, Ba and light rare earth elements. In common with other carbonatites, the Lofdal burbankite was variably affected by alteration to produce a complex secondary mineral assemblage. Different stages of burbankite alteration are observed, from completely fresh blebs and hexagonal crystals through to complete pseudomorphs, consisting of carbocernaite, ancylite, cordylite, strontianite, celestine, parisite and baryte. Although most research and exploration at Lofdal has focused on xenotime-bearing carbonatite dykes and wall-rock alteration, this complex also contains a more typical calcite carbonatite enriched in light rare earth elements and their alteration products.

Copper-sulfides within carbonatites and phoscorites of the Phalaborwa Igneous Complex, South Africa, have been investigated since the middle of the 20th Century. However, aspects of ore formation have remained unclear. This study examines the mechanisms involved in Cu-sulfide mineralisation by micro-focus X-ray computed tomography as applied to sulfide-rich drill core samples. Several texturally distinct assemblages of magmatic sulfides can be identified, including: (1) <500 μm rounded bornite and chalcopyrite grains disseminated within the gangue; (2) elongated mm-scale assemblages of chalcopyrite and bornite; and (3) mm-to-cm thick chalcopyrite cumulates. Chalcopyrite veins were also observed, as well as late-stage valleriite, documenting late-stage fluid circulation within the pipe, and alteration of magmatic and hydrothermal sulfides along fractures within the gangue, respectively. The results of micro-focus X-ray computed tomography indicate that magmatic sulfides are sub-vertically aligned. Spatial variability of the sulfide assemblages suggests that textural changes within sulfide layers reflect fluctuating magma flow rate during emplacement of carbonatite–phoscorite magmas, through coalescence or breakup of sulfide liquid droplets during ascent. Modal sulfide abundances, especially for disseminated assemblages, differ from one carbonatite–phoscorite layer to another, suggesting a strong control of the mechanical sorting in the formation of Cu-sulfide textures within the Loolekop carbonatite. The alternation of carbonatite and phoscorite within the intrusion suggest that the Loolekop Pipe was emplaced through a series of successive magma pulses, which differentiated into carbonatite and phoscorite by melt immiscibility/progressive fractional crystallisation and pressure drop. Three-dimensional textural analysis represents an effective tool for the characterisation of magma flow and is useful for the understanding of magmatic processes controlling sulfide liquid-bearing phoscorite–carbonatite magmas.

The Quaternary carbonatite–nephelinite Kerimasi volcano is located within the Gregory rift in northern Tanzania. It is composed of nephelinitic and carbonatitic pyroclastic rocks, tuffs, tuff breccias and pyroclastic breccias, which contain blocks of different plutonic (predominantly ijolite) and volcanic (predominantly nephelinite) rocks including carbonatites. The plutonic and volcanic carbonatites both contain calcite as the major mineral with variable amounts of magnetite or magnesioferrite, apatite and forsterite. Carbonatites also contain accessory baddeleyite, kerimasite, pyrochlore and calzirtite. Zr and Nb minerals are rarely observed in rock samples, though they are abundant in eluvial deposits of carbonatite tuff/pyroclastic breccias in the Loluni and Kisete craters. Pyrochlore, ideally (CaNa)Nb2O6F, occurs as octahedral and cubo-octahedral crystals up to 300 μm in size. Compositionally, pyrochlore from Loluni and Kisete differs. The former is enriched in U (up to 19.4 wt.% UO2), light rare earth elements (up to 8.3 wt.% LREE2O3) and Zr (up to 14.4 wt.% ZrO2), and the latter contains elevated Ti (up to 7.3 wt.% TiO2). All the crystals investigated were crystalline, including those with high U content (a = 10.4152(1) Å for Loluni and a = 10.3763(1) Å for Kisete crystals). They have little or no subsolidus alteration nor low-temperature cation exchange (A-site vacancy up to 1.5% of the site), and are suitable for single-crystal X-ray diffraction analysis (R1 = 0.0206 and 0.0290; for all independent reflections for Loluni and Kisete crystals, respectively). Observed variations in the pyrochlore composition, particularly Zr content, from the Loluni and Kisete craters suggest crystallisation from compositionally different carbonatitic melts. The majority of pyrochlore crystals studied exhibit exceptionally well-preserved oscillatory- and sometimes sector-type zoning. The preferential incorporation of smaller and higher charged elements into more geometrically constrained sites on the growing surfaces explains the formation of the sector zoning. The oscillatory zoning can be rationalised by considering convectional instabilities of carbonatite magmas during their emplacement.

Pyrochlore-group minerals are common accessory rare-metal bearing minerals in the calcite and ankerite carbonatites of the Amba Dongar complex (India). Pyrochlore from the Amba Dongar carbonatites differs from that in other Indian complexes in Ta, Zr, Ti, rare earth element (REE) and Pb contents, but is similar with respect to Ca, Ba and Sr abundances. The evolution of pyrochlore composition was studied to understand the alteration processes and the formation of late-stage pyrochlores enriched in REE and Pb. The early magmatic pyrochlore are calcio- and niobium-dominant types and were replaced by secondary cation-deficient varieties as a consequence of the action of hydrothermal fluids and supergene weathering. These processes produce changes mainly at the A site, rarely at the B site, and the original F is replaced by OH– groups. Calcium and Na can be extracted from the structure at the alteration stage and charge balance is achieved by the introduction of REE, Th, U, Ba or Sr. At the latest supergene stages, marginal and fractured zones of pyrochlore grains are altered to Pb-rich, Si-rich and cation-deficient hydrated varieties. The magmatic pyrochlore was crystallised in a highly alkaline environment at a high activity of Ca and at temperatures near 600°C, the alteration of pyrochlore began in a hydrothermal environment at temperatures below 350°C. The major compositional changes that are associated with the alteration are summarised by the following reactions: Ca2+ + Nb5+→ REE3+ + Ti4+; Nb5+ + Fe3+ → Ti4+ + Zr4+; and 2Nb5+ + Ca2+ → Ti4+ + Si4+ + U4+.

The Neoproterozoic Sevattur complex is composed essentially of calcite and dolomite carbonatites together with pyroxenites and diverse syenites. This work reports the compositions and paragenesis of different pyrochlore generations hosted by albitite veins in this complex. The pyrochlore are distinctive, being exceptionally rich in uranium (26 to 36 wt.% UO2). Five types of pyrochlore (Pcl-I to Pcl-V) are recognised on the basis of composition and texture. With the exception of Pcl-V, the majority of the pyrochlore (Pcl-II to Pcl-IV) are surrounded by a thick orbicular mantle of Ba-rich potassium feldspar. This mantle around Pcl-V is partially-broken. Pcl-I is restricted to the cores of crystals, and associated with Pcl-II and -III and is relatively rich in Nb (0.53–0.62 apfu) together with more A-site vacancies (0.37–0.71 apfu) compared to Pcl-II to Pcl-IV. Other pyrochlore (Pcl-II to Pcl-IV) are characterised by elevated Ca and Ti compared to Pcl-I, which are related to the (3Nb5+ + Na+ → 3Ti4+ + U4+) and (2Nb5+ → 2Ti4+ + Ca2+) substitutions, respectively. These substitutions represent replacement of Pcl-II to Pcl-IV. Alteration and Ba-enrichment in all the pyrochlore are marked by interaction with an externally-derived Ba-rich hydrothermal fluid following the (2Nb5+ → 2Ti4+ + Ba2+) substitution. This substitution, coupled with extensive metamictisation leads to the formation of Ba-rich (15.9–16.3 wt.% BaO) patchy-zoned Pcl-V. The orbicular mantles around Pcl-I to Pcl-IV have prevented extensive metamictisation and extensive secondary alteration compared to Pcl-V, where mantling is partially disrupted. The compositional and textural variation suggests that Pcl-II to Pcl-IV form by nucleation on Pcl-I, and are transported subsequently as antecrysts in the host albitite.

Pyrochlore-group minerals are common in the Neoproterozoic Sevattur carbonatite complex. This complex is composed of dolomite-, calcite-, banded- and blue carbonatite together with pyroxenite, albitite and diverse syenites. This work reports the paragenetic-textural types and compositional variation of pyrochlore hosted by dolomite carbonatite, banded carbonatite and albitite together with that of alteration assemblages containing belkovite and baotite. On the basis of composition, five different types of pyrochlore are recognised and termed Pcl-I through to Pcl-V. The Pb-rich Pcl-I are present exclusively as inclusions in U-rich Pcl-IIa in dolomite carbonatite. The alteration assemblages of Pb-poor Pcl-IIb + Ba-rich or Ba–Si- rich Pcl-IV + belkovite (dolomite carbonatite) and Si-rich Pcl-V + baotite (banded carbonatite) formed after Pcl-IIa differ in these carbonatites. The albitite hosts extremely U-Ti-rich Pcl-III, mantled by Ba-rich potassium feldspar. In common with the banded carbonatite, Pcl-V is formed by alteration of Pcl-III where this mantle is partially, or completely broken. The Ba-Si-enrichment of Pcl-IV and Pcl-V together with the ubiquitous presence of baryte in all Sevattur lithologies suggests late-stage interaction with a Ba-Si-rich acidic hydrothermal fluid. This fluid was responsible for leaching silica from the associated silicates and produced Pcl-V in the silicate-rich lithologies of the banded carbonatite and albitite. The absence of Pcl-V in dolomite carbonatite is a consequence of the low modal abundance of silicates. The complex compositional diversity and lithology specific pyrochlore alteration assemblages suggest that all pyrochlore (Pcl-I to Pcl-IV) were formed initially in an unknown source and transported subsequently in their respective hosts as altered antecrysts.

Microporous slicates with the pharmacosiderite structure and the general formula A3–xH1+x[Ti4O4(SiO4)3](H2O)n (A = Na, K, Cu), (n = 6–9, x = 0–2) are outstanding in their ion-exchange properties. The ivanyukite mineral group consists of three species, one of which has two polymorphs. The minerals forming a progressive series: ivanyukite-Na-T → ivanyukite-Na-C → ivanyukite-K → Cu-rich ivanyukite-K → ivanyukite-Cu, have been studied by single-crystal X-ray diffraction, electron microprobe analysis and Raman spectroscopy. The microporous heteropolyhedral framework of the ivanyukite-group minerals is based on cubane-like [Ti4O4]8+ clusters that share common corners with SiO4 tetrahedra to form wide three-dimensional channels suitable for the migration of Na+, K+ and Cu2+ ions. Ivanyukite-Na-T that has a R3m symmetry loses Na+ in aqueous solutions via the substitution Na+ + O2‒ ↔ □ + OH‒, which allows for the migration of K+ ions and transformation of initial structure into the cubic (P$\bar{4}3m$) ivanyukite-Na-C polymorph or into ivanyukite-K, when most of Na is lost. Natural ivanyukite-Na-C is shown to contain domains of both R3m (subordinate) and P$\bar{4}3m$ (dominant) symmetry with the chemical composition determining the stability and dominance of cubic or trigonal forms. Incorporation of Cu into the crystal structure ivanyukite-K via the substitution K+ + OH− ↔ Cu2+ + O2− in aqueous solutions results in the formation of ivanyukite-Cu. Post-crystallisation processes (such as exchange of Na+, K+, Cu2+, and/or hydration/dehydration of primary phases) are widespread in hyperagpaitic rocks of the Kola alkaline massif and the respective mineral transformations contribute to the diversity of mineral species.

The crystal structure of nikmelnikovite, Ca12Fe2+Fe3+3Al3(SiO4)6(OH)20, a new member of the garnet supergroup from Kovdor massif, Kola Peninsula, Russia (R$\bar{3}$, a = 17.2072(6), c = 10.5689(4) Å, V = 2710.1(2) Å3 and Z = 3) has been refined to R1 = 0.046 on the basis of 1184 unique observed reflections. Nikmelnikovite is the first mineral species in the garnet supergroup that has a trigonal (rhombohedral) symmetry. The relationship between its unit cell and the pseudocubic (ideal garnet) unit cell can be described by the transformation matrix [1$\bar{1}$0 | 01$\bar{1}$ | ½½½]. The crystal-chemical relations between the ideal Ia$\bar{3}$d garnet and the nikmelnikovite structure type can be described by the following series of imaginary modifications: (1) the symmetry is lowered according to the Ia$\bar{3}$d → R$\bar{3}$ group–subgroup relationship; (2) the cation sites are split according to the following sequences: X → {X1, X2}; Y → {Y1, Y2, Y3, Y4}; Z → {Z1, Z2}; (3) the X sites remain fully occupied by Ca; (4) each Y site is occupied predominantly by a distinct chemical species: Y1 → Al (Al site), Y2 → Fe2+ (Fe1 site), Y3 → Fe3+ (Fe2 site), Y4 → vacancy (Mn site); (5) one of the Z sites (Z1) is occupied by Si, whereas the other site (Z2) is predominantly vacant. The crystal-chemical formula that takes into account the transition between the archetype and the nikmelnikovite structure type can be described as X{Ca12}Y[Fe2+Al4Fe3+2□]Z(Si6□6)O24(OH)20□4. The structural complexity of nikmelnikovite (4.529 bit/atom and 434.431 bit/cell, after H-correction) is higher than those for andradite, grossular and katoite, which is typical for low-temperature minerals formed after primary minerals with simpler structures.

An unusual highly hydrated and Na-depleted variety of elpidite was identified in a hydrothermally altered peralkaline pegmatite at Mt. Yukspor in the Khibiny alkaline complex, Kola Peninsula, Russia. It differs from ‘ordinary’ elpidite, ideally Na2ZrSi6O15⋅3H2O, in its crystal chemical features, infrared spectrum and optical characteristics. The chemical composition (wt.%, electron microprobe, H2O by TGA) is: Na2O 5.45, K2O 0.67, CaO 0.05, SiO2 60.32, TiO2 1.34, ZrO2 18.43, Nb2O5 0.65, H2O 12.80, total 99.71. The empirical formula calculated on the basis of 6 Si and 15 O atoms is [(Na1.05K0.08Ca0.01)Σ1.14(H3O)0.74]Σ1.88(Zr0.89Ti0.10Nb0.03)Σ1.02Si6O15⋅3.47H2O; the H2O:H3O ratio was calculated from the charge balance requirement, taking into account the results of crystal structure refinement. The highly hydrated variety of elpidite is orthorhombic, Pma2, a = 14.5916(6), b = 7.3294(3), c = 7.1387(2) Å, V = 763.47(5) Å3 and Z = 2. The crystal structure was solved from single-crystal X-ray diffraction data, R1 = 3.43%. The structure is based upon an elpidite-type heteropolyhedral Zr–Si–O framework with Na+ and H3O+ cations and H2O molecules in the zeolitic channels. Hydronium cations substitute for water molecules in one of the extra-framework sites. This variety of elpidite could be considered as an intermediate product of natural ion-exchange reaction between ‘ordinary’ elpidite and a low-temperature hydrothermal fluid.