Zoning texture in sphalerite has been described in many studies, although its genesis and ore formation process are poorly constrained. In this investigation, we compare the in situ trace element and isotopic composition of colour-zoned sphalerites from Nayongzhi, South China, to explain the zoning growth process. Petrographic observations identified two broad types of zoned sphalerite, core–rim (CR) and core–mantle–rim (CMR) textures. Each zoned sphalerite displays two or three colour zones, including brown core, light colour bands and/or pale-yellow zones. In situ laser ablation inductively coupled plasma mass spectrometry trace-element analyses show that the three colour zones display variable trace-element compositions. Brown cores exhibit distinctly high Mn, Fe, Co, Ge, Tl and Pb concentrations, whereas pale-yellow and light colour zones have elevated Ga, Cd, Sn, In and Sb concentrations. Copper, Sb, In and Sn show slight variations between pale-yellow and light zones, the latter having higher In and Sn, but lower Cu and Sb abundances. Given the low concentration range of Pb, Ge, Tl, Mn Sb, Cd, etc., the colour of sphalerite is attributed mainly to Fe compositional variation. The δ34S values of sphalerite from Nayongzhi range from +22.3 to +27.9‰, suggesting reduced sulfur was generated by thermochemical sulfate reduction of marine sulfate in ore-hosted strata. Single-crystal colour-zoned sphalerite exhibits intracrystalline δ34S variation (up to 4.3‰), which is attributed to the δ34S composition of H2S in the original fluid. The lack of correlation between trace elements and δ34S values indicates episodic ore solution influxes and mixes with the reduced sulfur-rich fluid derived from the aquifers of the ore-hosted strata, which play a key role in the formation of the zoned Nayongzhi sphalerite. In conclusion, in situ trace element and S isotope studies of zoned sphalerite crystals might provide insight into the ore-forming process of MVT deposits.

The new mineral hrabákite (IMA2020-034) was found in siderite–sphalerite gangue with minor dolomite–ankerite at the dump of shaft No. 9, one of the mines in the abandoned Příbram uranium and base-metal district, central Bohemia, Czech Republic. Hrabákite is associated with Pb-rich tučekite, Hg-rich silver, stephanite, nickeline, millerite, gersdorffite, sphalerite and galena. The new mineral occurs as rare prismatic crystals up to 120 μm in size and allotriomorphic grains. Hrabákite is grey with a brownish tint. Mohs hardness is ca. 5–6; the calculated density is 6.37 g.cm–3. In reflected light, hrabákite is grey with a brown hue. Bireflectance is weak and pleochroism was not observed. Anisotropy under crossed polars is very weak (brownish tints) to absent. Internal reflections were not observed. Reflectance values of hrabákite in air (Rmin–Rmax, %) are: 39.6–42.5 at 470 nm, 45.0–47.5 at 546 nm, 46.9–49.2 at 589 nm and 48.9–51.2 at 650 nm). The empirical formula for hrabákite, based on electron-microprobe analyses (n = 11), is (Ni8.91Co0.09Fe0.03)9.03(Pb0.94Hg0.04)0.98(Sb0.91As0.08)0.99S7.99. The ideal formula is Ni9PbSbS8, which requires Ni 47.44, Pb 18.60, Sb 10.93 and S 23.03, total of 100.00 wt.%. Hrabákite is tetragonal, P4/mmm, a = 7.3085(4), c = 5.3969(3) Å, with V = 288.27(3) Å3 and Z = 1. The strongest reflections of the calculated powder X-ray diffraction pattern [d, Å (I)(hkl)] are: 3.6543(57)(200); 3.2685(68)(210); 2.7957(100)(211); 2.3920(87)(112); 2.3112(78)(310); 1.8663(74)(222); and 1.8083(71)(302). According to the single-crystal X-ray diffraction data (Rint = 0.0218), the unit cell of hrabákite is undoubtedly similar to the cell reported for tučekite. The structure contains four metal cation sites, two Sb (Sb1 dominated by Pb2+) and two Ni (with minor Co2+ content) sites. The close similarity in metrics between hrabákite and tučekite is due to similar bond lengths of Pb–S and Sb–S pairs. Hrabákite is named after Josef Hrabák, the former professor of the Příbram Mining College.

Native tungsten (IMA2011-004), W, is officially described as a new mineral from gold placers in the Bol'shaya Pol'ya river valley, Prepolar Urals, Russia, associated with yttriaite-(Y) and from quartz veins in the Mt Neroyka rock-crystal field, Ust–Puiva, Tyumenskaya Oblast', Russia. Tungsten forms polycrystalline grains and masses, and rarely cubo-octahedra. It is silver white to steel grey in colour, with metallic lustre and grey streak. The calculated density is 19.226 g/cm3. The Vickers hardness (VHN25) is 571.45 kg/mm2. In plane polarised light, tungsten is white with a pale-yellow tint and optically isotropic. Electron microprobe analyses of Bol'shaya Pol'ya river valley material provided W 99.27, Mo 0.06, Mn 0.04, Fe 0.01, total 99.38 wt.%. The five strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 2.2422(100)(110), 1.5835(25)(200), 1.2929(48)(211), 1.0010(23)(310) and 0.8457(24)(321). Tungsten is cubic, Im$\bar{3}$m, a = 3.1648(4) Å, V = 31.69(4) Å3 and Z = 2. Some additional occurrences of native tungsten and technogenic tungsten found in Nature are also described.

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.

Tennantite-(Hg), Cu6(Cu4Hg2)As4S13, was approved as a new mineral species (IMA2020-063) from the Lengenbach quarry, Imfeld, Binn Valley, Canton Valais, Switzerland. It was identified as an aggregate of black metallic tetrahedral crystals, less than 0.1 mm in size, intimately associated with sinnerite, and grown on realgar. In reflected light, tennantite-(Hg) is isotropic, grey in colour, with creamy tints. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 470: 29.1; 546: 29.1; 589: 28.5; 650: 27.7. Electron microprobe analysis gave (in wt.% – average of 7 spot analyses): Cu 32.57(42), Ag 6.38(19), Tl 0.29(14), Zn 0.04(5), Hg 17.94(2.27), Pb 0.70(51), As 17.83(61), Sb 0.34(8), S 24.10(41), total 100.19(1.04). The empirical formula of the sample studied, recalculated on the basis of ΣMe = 16 atoms per formula unit, is (Cu4.69Ag1.04Tl0.03)Σ5.76(Cu4.35Hg1.58Pb0.06Zn0.01)Σ6.00(As4.20Sb0.05)Σ4.25S13.26. Tennantite-(Hg) is cubic, I$\overline 4$3m, with a = 10.455(7) Å, V = 1143(2) Å3 and Z = 2. The crystal structure of tennantite-(Hg) has been refined by single-crystal X-ray diffraction data to a final R1 = 0.0897 on the basis of 214 unique reflections with Fo > 4σ(Fo) and 22 refined parameters. Tennantite-(Hg) is isotypic with other members of the tetrahedrite group. Mercury is hosted at the tetrahedrally coordinated M(1) site, in accord with the relatively long M(1)–S(1) distance (2.389 Å), similar to that observed in tetrahedrite-(Hg). Minor Ag is located at the triangularly-coordinated and split M(2) site. Other occurrences of tennantite-(Hg) are briefly reviewed and the Lengenbach finding is described within the framework of previous knowledge about the Hg mineralogy at this locality.

Scar Crags and Dale Head North in the English Lake District host mineralised veins enriched in ‘Energy Critical Elements’ (ECEs) specifically, bismuth, cobalt and copper. A limited number of studies in the 1970s investigated the mineralogy and inferred the genesis of these veins as being related to the intrusion of the Lake District batholith.

This study investigates the geology, mineralogy, composition and paragenesis of these two mineralised areas. The results highlight the ubiquitous presence of Co–Fe–Ni-sulfarsenides in both deposits and the presence of some mineral species, hitherto unreported. Scar Crags samples contained high concentrations of cobalt, commonly present within arsenopyrite, whereas cobalt is of minor importance at Dale Head North, where copper and arsenic are the primary metals. A sequence of events, with As–Co–Ni-bearing fluids infilling the veins after an initial stage of quartz and chlorite precipitation is the most striking resemblance between the two mineralised systems, potentially indicating a common process for Co-rich vein-type deposits in the area. If so, understanding such processes could prove vital in aiding exploration in other terranes.

Thebaite-(NH4), (NH4,K)3Al(C2O4)(PO3OH)2(H2O), is a new mineral species (IMA2020-072) from the Rowley mine, Maricopa County, Arizona, USA. It occurs in an unusual bat-guano-related, post-mining assemblage of phases that include a variety of vanadates, phosphates, oxalates and chlorides, some containing NH4+. Other secondary minerals found in association with thebaite-(NH4) are antipinite, vanadinite and at least one other new mineral. Crystals of thebaite-(NH4) are colourless blades up to ~0.1 mm in length. The streak is white, lustre is vitreous, Mohs hardness is 1½–2, tenacity is brittle and fracture is splintery. There are two good cleavages in the [010] zone, probably {100} and {10$\bar{2}$}. The calculated density is 2.093 g⋅cm–3. Thebaite-(NH4) is optically biaxial (–) with α = 1.490(2), β = 1.534(2), γ = 1.570(2) (white light); 2V = 82.7(5)°; slight r > v dispersion; and orientation X = b, Y ^ c = 13° in obtuse β. Electron microprobe analysis gave the empirical formula [(NH4)2.12K0.69Na0.20]Σ3.01(Al0.84Fe3+0.11V3+0.04)Σ0.99(C2O4)[(P0.98Si0.02)O3OH]2(H2O), with the C, N and H contents constrained by the crystal structure. Raman spectroscopy confirmed the presence of NH4 and C2O4. Thebaite-(NH4) is monoclinic, P21/c, with a = 11.156(9), b = 6.234(6), c = 18.651(16) Å, β = 102.928(15)°, V = 1264.2(19) Å3 and Z = 4. The structural unit in the crystal structure of thebaite-(NH4) (R1 = 0.0612 for 863 Io > 2σI reflections) is a double-strand chain of corner-sharing AlO6 octahedra and PO3OH tetrahedra decorated by additional PO3OH tetrahedra and C2O4 groups. The decorated chains connect to one another through bonds to NH4+ and K+ and through hydrogen bonds.

A common attribute of two rare natural chromium-bearing oxides: mcconnellite, CuCrO2, discovered more than 40 years ago in Guyana, and a new mineral ellinaite, CaCr2O4, described from two localities (Brazil and Israel) recently, is that these minerals are poorly studied due to their rarity and small size. Mcconnellite and ellinaite in the present study were found in varicoloured marbles of the pyrometamorphic Hatrurim Complex in the Tulul Al Hammam area, Daba-Siwaqa, Jordan. Structural data obtained for ellinaite (Pnma, a = 9.0875(2), b = 2.9698(1), c = 10.6270(3) Å and V = 286.80(2) Å3), with an empirical formula (Сa1.00Sr0.01)Σ1.01(Cr3+1.79Al0.07Ca0.04Fe3+0.04 Ti4+0.03Mg0.03)Σ2.00O4, is similar to the structural data of synthetic analogue β-CaCr2O4 but differs significantly from the data obtained for ellinaite from Brazil and Israel despite the fact that all the natural phases have a similar composition. Single-crystal X-ray diffraction data for mcconnellite from Jordan (R$\bar{3}$m, a = b = 2.9756(1) and c = 17.124(1) Å) with composition (Cu0.98Ca0.03Sr0.01)Σ1.02(Cr3+0.90Al0.05 Fe3+0.03)Σ0.98O2, is the first determination of a natural Cu-delafossite-type structure. This paper also presents the results of a single-crystal Raman study for mcconnellite and ellinaite, which indicates that the spectral features of these minerals is dependent on crystal orientation.

Rare earth elements (REEs, ‘lanthanides’) constitute a vital commodity for technological applications. Although these elements occur at trace levels in many minerals, they can comprise major constituents of low abundance phosphate, carbonate, silicate and oxide minerals, some of which form during granite weathering. REE-phosphate phases can be a source of phosphorus for essential biomolecules and certain REEs are required by some bacterial enzymes involved in the oxidation of methanol, an important compound in the global biogeochemical carbon cycle. The mechanisms that promote the dissolution of lanthanide phosphate minerals are largely unknown, but probably vary with the lanthanide phosphate mineralogy of weathered rock and soil. Here, we studied weathering of five I-type, three S-type and one A-type granite to determine the extent of weathering of primary REE- and/or P-bearing minerals apatite, allanite and monazite, and the formation of secondary REE/P-bearing minerals. We found evidence for greater mobilisation of REE and P in weathered I-type and A-type granites than in S-types, reflecting the higher solubility of apatite and allanite relative to monazite. Although monazite persisted in highly weathered S-type granites, some alteration was detected. Secondary REE/P-bearing minerals were not detected in two S-type profiles, while spherical secondary REE/P-bearing mineral aggregates were abundant throughout the third S-type profile. Secondary euhedral REE/P-bearing crystals were abundant even in the slightly weathered I-type and A-type granite material, yet they were not detected in the highly weathered material, indicating that these minerals had dissolved. Our findings indicate that mineralogy constrains substantially, but does not control completely, lanthanide availability as a function of degree of weathering. These results have implications for predicting REE and phosphate bioavailability in soils derived from granitic rock types and suggest that highly weathered I-type granites may provide inocula for bioleaching experiments.

Hydrothermally synthesised K2ZnSi5O12 has a polymerised framework structure with the same topology as leucite (KAlSi2O6, tetragonal I41/a), which has two tetrahedrally coordinated Al3+ cations replaced by Zn2+ and Si4+. At 293 K it has a cation-ordered framework P21/c monoclinic structure with lattice parameters a = 13.1773(2) Å, b = 13.6106(2) Å, c = 13.0248(2) Å and β = 91.6981(9)°. This structure is isostructural with K2MgSi5O12, the first cation-ordered leucite analogue characterised. With increasing temperature, the P21/c structure transforms reversibly to cation-ordered framework orthorhombic Pbca. This transition takes place over the temperature range 848−863 K where both phases coexist; there is an ~1.2% increase in unit cell volume between 843 K (P21/c) and 868 K (Pbca), characteristic of a first-order, displacive, ferroelastic phase transition. Spontaneous strain analysis defines the symmetry- and non-symmetry related changes and shows that the mechanism is weakly first order; the two-phase region is consistent with the mechanism being a strain-related martensitic transition.

The new alluaudite-group mineral calciojohillerite is one of the major arsenates in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. In middle zones of the fumarole, calciojohillerite is associated with hematite, tenorite, johillerite, nickenichite, bradaczekite, badalovite, tilasite, lammerite, ericlaxmanite, aphthitalite-group sulfates, langbeinite, calciolangbeinite, anhydrite, sanidine, fluorophlogopite, fluoborite, cassiterite, pseudobrookite, rutile, sylvite and halite. In deep zones it occurs in association with anhydrite, diopside, hematite, svabite, berzeliite, schäferite, forsterite, magnesioferrite, ludwigite, rhabdoborite-group fluoroborates, powellite, baryte, fluorapatite, udinaite, arsenudinaite and paraberzeliite. Calciojohillerite forms prismatic crystals up to 1 cm long, their aggregates and crystal crusts up to 0.5 m2. It is transparent, colourless, pale green, pale yellow, light blue, pale lilac or pink, with vitreous lustre. The mineral is brittle, with imperfect cleavage. The Mohs hardness is 3½. Dcalc is 3.915 g cm–3. Calciojohillerite is optically biaxial (–), α = 1.719(3), β = γ = 1.732(3); 2Vmeas. = 15(10)°. Chemical composition (wt.%, electron-microprobe; holotype) is: Na2O 7.32, K2O 0.10, CaO 6.82, MgO 20.31, MnO 0.68, CuO 0.27, ZnO 0.02, Al2O3 0.56, Fe2O3 3.53, TiO2 0.01, SiO2 0.03, P2O5 1.25, V2O5 0.10, As2O5 58.77, SO3 0.13, total 99.90. The empirical formula based on 12 O atoms is (Na1.30K0.01Ca0.67Mg2.78Mn0.05Cu0.02Al0.06Fe3+0.24)Σ5.13(As2.83P0.10S0.01V0.01)Σ2.95O12. Calciojohillerite is monoclinic, C2/c, a = 11.8405(3), b = 12.7836(2), c = 6.69165(16) Å, β = 112.425(3)°, V = 936.29(4) Å3 and Z = 4. The crystal structure was solved from single-crystal X-ray diffraction data, R1 = 0.0227. Calciojohillerite is isostructural with other alluaudite-group minerals. Its simplified crystal chemical formula is A(1)CaA(1)′□A(2)□A(2)′NaM(1)MgM(2)Mg2(AsO4)3 (□ = vacancy). The idealised formula is NaCaMg3(AsO4)3, or, according to the nomenclature of alluaudite-group arsenates, NaCaMgMg2(AsO4)3. Calciojohillerite is named as an analogue of johillerite NaCu2+MgMg2(AsO4)3 with species-defining Ca instead of Cu in the ideal formula.

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.

Golden perch (Macquaria ambigua) is a freshwater game-fish native to central and southeast Australia. Larvae of this fish species were used in two different types of experiments to evaluate the effects of short-term exposures (up to 6 days) to aqueous gold, 5 nm gold nanoparticles (AuNPs), or 50 nm AuNPs. Relative to the control, increased gold concentrations corresponded with yolk-sac edema (swelling). Larvae exposed to 50 μM of 5 nm AuNPs had yolk-sacs that were ~1.5 times larger resulting in the appearance of bent notochords. After two days of exposure, 100% mortality was observed. Total mortalities were <25% in the other larvae–gold systems, suggesting that these larvae can quickly adapt to the presence of gold. In terms of an oxidative stress response, the larvae from all systems did not express high enzymatic activity. The state of the gold determined how much could be taken up (or immobilised) by a larva. Aqueous gold and 5 nm AuNPs easily pass through cells; therefore, larvae exposed to these forms of gold contained the highest concentrations. Scanning electron microscopy confirmed that cells comprising the epithelium and fins contained AuNPs. Aqueous gold was reduced to nanometre-scale particles within cells. Comparatively, 5 nm AuNPs appeared to be aggregated within cells forming clusters hundreds of nanometres in size. On the contrary, 50 nm AuNPs were not observed within cells but were detected within larvae by (single particle) inductively coupled plasma mass spectroscopy, suggesting that these AuNPs were probably taken up through the mouth or gills. The results of the present study demonstrate that exposure to AuNPs had adverse effects on developing golden perch larvae. Additionally, these effects were dependent on the size of the AuNPs.

The margarosanite group (now officially confirmed by IMA-CNMNC) consists of triclinic Ca-(Ba, Pb) cyclosilicates with three-membered [Si3O9]6– rings (3R), with the general formula AB2Si3O9, where A = Pb, Ba and Ca and B = Ca. A closest-packed arrangement of O atoms parallel to (101) hosts Si and B cations in interstitial sites in alternating layers. The 3R layer has three independent Si sites in each ring. Divalent cations occupy three independent sites: Ca in B occupies two nonequivalent sites, Ca1 (8-fold coordinated), and Ca2 (6-fold coordinated). A (=Ca3) is occupied by Pb2+ (or Ba2+) in 6+4 coordination, or 6+1 when occupied by Ca; this third site occurs within the 3R-layer in a peripheral position. Three minerals belong to this group: margarosanite (ideally PbCa2Si3O9), walstromite (BaCa2Si3O9) and breyite (CaCa2Si3O9). So far, no solid solutions involving the Ca1 and Ca2 sites have been described. Therefore, root names depend on the composition of the Ca3 site only. Isomorphic replacement at the Ca3 sites has been noted. We here report data on a skarn sample from the Jakobsberg Mn–Fe oxide deposit, in Värmland, Sweden, representing intermediate compositions on the walstromite–margarosanite binary, in the range ca. 50–70% mol.% BaCa2Si3O9. The Pb-rich walstromite is associated closely with celsian, phlogopite, andradite, vesuvianite, diopside and nasonite. A crystal-structure refinement (R1 = 4.8%) confirmed the structure type, and showed that the Ca3 (Ba, Pb) site is split into two positions separated by 0.39 Å, with the Ba atoms found slightly more peripheral to the 3R-layers.

The new högbomite-group mineral magnesiohögbomite-6N12S, ideally Mg5Al11TiO23(OH), was found in calcite “vein-dikes” at the DeWitts Corners occurrence, lots 10 and 11, concession 1, Bathurst Township, Ontario, Canada. It forms tabular and short-prismatic crystals up to 5 mm in size. The major forms are pinacoid {0001} and hexagonal pyramid {11${\bar 2}$1}, sometimes modified by hexagonal prism {11${\bar 2}$0}. The associated minerals are magnesiohögbomite-2N3S, spinel, corundum, diopside, magnesio-hastingsite, pargasite, clinochlore and calcite. Magnesiohögbomite-6N12S is dark brown to black with brown streak and vitreous lustre. It has no cleavage and its fracture is uneven. The Mohs hardness is 6½. Dcalc is 3.87 g/cm3. The infrared spectrum is reported. The composition (wt.%) is MgO 13.09, ZnO 0.46, FeO 11.91, Fe2O3 6.84, Al2O3 62.70, TiO2 4.44, H2O 0.99, total 100.43. The empirical formula calculated on the basis of 17 cations, excluding H+, is (Mg2.95Fe2+1.51Al0.49Zn0.05)Σ5(Al10.71Fe3+0.78Ti0.51)Σ12O23(OH). The simplified formula is (Mg,Fe)5(Al,Fe,Ti)12O23(OH). The mineral is trigonal, R${\bar 3}$m, a = 5.7194(2), c = 83.069(5) Å, V = 2353.3(2) Å3 and Z = 6. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are: 2.921(26)(0.1.23), 2.863(49)(110), 2.687(29)(0.1.26), 2.547(31)(0.1.$\overline{28}$) and 2.434(100)(1.1.18). The crystal structure was solved and refined from single-crystal X-ray diffraction data to R1 = 0.022. It is composed of alternating spinel (S) and nolanite (N) modules in the sequence 3 × (NSSNSS). The sequence of cubic ‘c’ and hexagonal ‘h’ closed-packed oxygen layers is 3 × (cccccchcccch). It is the first polysome in the högbomite supergroup with such a sequence.

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.

Three new isostructural minerals, alexkuznetsovite-(La), ideally La2Mn(CO3)(Si2O7), alexkuznetsovite-(Ce) Ce2Mn(CO3)(Si2O7) and biraite-(La) La2Fe2+(CO3)(Si2O7), were discovered in polymineralic nodules from the Mochalin Log REE deposit, South Urals, Russia. The new minerals form anhedral grains up to 0.3 mm × 0.4 mm [alexkuznetsovite-(La)], 0.5 mm × 0.9 mm [alexkuznetsovite-(Ce)] and 0.2 mm × 1.2 mm [biraite-(La)] embedded in granular aggregates consisting of different REE minerals [allanite-(Ce)/-(La), bastnäsite-(Ce)/-(La), fluorbritholite-(Ce), perbøeite-(Ce)/-(La), percleveite-(Ce)/-(La) and törnebohmite-(Ce)/-(La)]. All three new species are brown to dark brown, translucent in thin fragments, with white streak, vitreous lustre and Mohs’ hardness of ~5. Dcalc = 4.713 [alexkuznetsovite-(La)], 4.687 [alexkuznetsovite-(Ce)] and 4.682 [biraite-La)] g⋅cm–3. Their empirical formulae, calculated on the basis of 2 Si and 10 O apfu, are: alexkuznetsovite-(La): (La0.98Ce0.89Nd0.10Pr0.05)Σ2.02Mn2+0.50Fe2+0.29Ca0.12Mg0.03(CO3)0.94(HCO3)0.06 (Si2O7); alexkuznetsovite-(Ce): (Ce0.96La0.78Nd0.16Pr0.07)Σ1.97Th0.01Mn2+0.50Fe2+0.33Ca0.14Mg0.02(CO3)0.93(HCO3)0.07(Si2O7); and biraite-(La): (La0.95Ce0.87Nd0.08Pr0.04)Σ1.94Th0.01Ca0.12Fe2+0.44Mn2+0.38Mg0.07(CO3)0.88(HCO3)0.12(Si2O7). The new minerals are monoclinic, P21/c and Z = 4. The unit-cell parameters of alexkuznetsovite-(La)/alexkuznetsovite-(Ce)/biraite-(La) are: a = 6.5642(3)/6.5764(4)/6.5660(10), b = 6.7689(3)/6.7685(4)/6.7666(11), c = 18.7213(10)/18.7493(15)/18.698(3) Å, β = 108.684(6)/108.672(8)/108.952(16)° and V = 788.00(7)/790.66(10)/785.7(2) Å3. The crystal structures are solved from single-crystal X-ray diffraction data; R = 0.0628 [alexkuznetsovite-(La)], 0.0589 [alexkuznetsovite-(Ce)] and 0.1193 [biraite-(La)]. A new biraite group is defined; it includes isostructural biraite-(Ce) and the three new minerals described herein. The rootname alexkuznetsovite is given in honour of the Russian mineral collector Alexey M. Kuznetsov (born 1962) who provided samples in which all three new minerals were found. The Levinson's suffix-modifier -(La) or -(Ce) indicates the predominance of La or Ce among REE in the mineral. Biraite-(La) is named as an analogue of biraite-(Ce) with La prevailing among REE.