Rundqvistite-(Ce), ideally Na3(Sr3Ce)(Zn2Si8O24), is a new mineral from the Darai-Pioz alkaline massif, Tien-Shan Mountains, Tajikistan. The mineral occurs as elongated grains up to 0.1 mm long and up to 0.03 mm thick embedded in quartz–pectolite aggregate in a silexite-like peralkaline pegmatite. Associated minerals are quartz, fluorite, pectolite, baratovite, aegirine, leucosphenite, neptunite, reedmergnerite, orlovite, sokolovaite, mendeleevite-(Ce), odigitriaite, pekovite, zeravshanite, kirchhoffite and garmite. The mineral is colourless with a vitreous lustre and a white streak, brittle, Dmeas. is 3.70(2) and Dcalc. is 3.709 g/cm3. Rundqvistite-(Ce) is monoclinic, space group P21/c, a = 5.1934(16), b = 7.8934(16), c = 26.011(5) Å, β = 90.02(3)° and V = 1066.3(4) Å3. The chemical composition of rundqvistite-(Ce) is SiO2 40.17, La2O3 2.64, Ce2O3 7.55, Pr2O3 0.80, Nd2O3 2.43, Sm2O3 0.33, Eu2O3 0.09, Gd2O3 0.24, Tb2O3 0.18, Dy2O3 0.21, PbO 1.03, SrO 19.83, FeO 0.37, ZnO 13.08, CaO 2.55, Na2O 8.04, total 99.54 wt.%. The empirical formula calculated on 24 O apfu (atoms per formula unit) is Na3.10Sr2.29Ca0.54Pb0.06(Ce0.55La0.19Nd0.17Pr0.06Sm0.02Gd0.02Eu0.01Tb0.01Dy0.01)Σ1.04Zn1.92Fe0.06 Si8.00O24 Z = 2. The structural formula based on refined site-occupancies is (Na2.94Sr0.06)Σ3.00 [(Sr2.23Ca0.54Pb0.06Na0.13)Σ2.96Ln3+1.04]Σ4.00[(Zn1.92Fe2+0.06)Σ1.98Si8O24], where Ln3+1.04 = (Ce0.55La0.19Nd0.17Pr0.06Sm0.02Gd0.02Eu0.01Tb0.01Dy0.01)Σ1.04. The crystal structure of rundqvistite-(Ce) was refined to R1 = 2.76% on the basis of 3184 unique reflections [F > 4σ|F|]. In rundqvistite-(Ce), the main structural unit is a (Zn2Si8O24)12– sheet parallel to (100). In the sheet, the Si and Zn tetrahedra form four-, five- and eight-membered rings. The interstitial cations at the Na and M(1–3) sites sum to [Na3(Sr3Ce)]12– apfu. The Na and M(1–3) polyhedra share common edges to form a layer. Rundqvistite-(Ce) is a structural analogue of vladykinite, ideally Na3Sr4(Fe2+Fe3+)Si8O24. Rundqvistite-(Ce) and vladykinite are related by the following substitution: [8]Ce3+ + [4](Zn2+)2 ↔ [8]Sr2+ + [4](Fe2+Fe3+). The mineral is named after Dmitry Vasilievich Rundqvist (1930–2022), a prominent Russian geologist and an expert on the geology of ore deposits, metallogeny and mineralogy of Precambrian rocks.

Xenotime-(Gd), ideally GdPO4, is a new mineral of the xenotime group. It was discovered at the Zimná Voda REE–U–Au occurrence near Prakovce, Western Carpathians, Slovakia. It forms rare crystal domains (≤20 μm, usually ≤10 μm in size) in Gd-rich xenotime-(Y) crystals (≤100 μm in size), in association with monazite-group minerals, uraninite, fluorapatite and uranyl arsenates–phosphates. The hydrothermal REE–U–Au mineralisation occurs in a quartz–muscovite vein, hosted in Palaeozoic phyllites near exocontact with Permian granites. The density is 5.26 g/cm3, based on calculated average empirical formula and unit-cell parameters. The average chemical composition (n = 6) measured by electron microprobe is as follows (wt.%): P2O5 30.1, As2O5 0.5, SiO2 0.2, UO2 0.3, Y2O3 15.7, (La, Ce, Pr, Nd)2O3 0.5, Sm2O3 5.7, Eu2O3 1.4, Gd2O3 29.2, Tb2O3 3.9, Dy2O3 10.4, Ho2O3 0.4, (Er, Tm, Yb, Lu)2O3 2.1, (Ca, Fe, Pb, Mn, Ba)O 0.1, total 100.5. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.37Y0.32Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Tm0.01Nd0.01…)Σ1.01(P0.98As0.01Si0.01)O4. The empirical formula of the Gd-richest composition is: (Gd0.38Y0.31Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Nd0.01Ho0.01…)Σ1.01(P0.98As0.01Si0.01)O4. The ideal formula is GdPO4. The xenotime-type structure has been confirmed by micro-Raman spectroscopy and a Fast Fourier-Transform pattern using HRTEM. Xenotime-(Gd) is tetragonal, space group I41/amd, a = 6.9589(5) Å, c = 6.0518(6) Å, V = 293.07(3) Å3 and Z = 4. The new mineral is named as an analogue of xenotime-(Y) and xenotime-(Yb) with Gd dominant among the REE. The middle REE enrichment of xenotime-(Gd) is shared with the associated monazite-(Gd) and Gd-rich hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing minerals is a product of selective complexing and enrichment in MREE in low-temperature hydrothermal fluids by alteration of uraninite, brannerite and fluorapatite on a micro-scale. The existence of xenotime-(Gd) and monazite-(Gd) is the first naturally documented dimorphism among REE phosphates. In addition, xenotime-(Gd) is only the third approved Gd-dominant mineral, after lepersonnite-(Gd) and monazite-(Gd).

Hakite-(Cd), hakite-(Fe) and hakite-(Zn) are new minerals belonging to the tetrahedrite group and forming, along with hakite-(Hg), the hakite series. They have been discovered in samples collected from the Bytíz deposit, in the uranium and base-metal Příbram ore district, Central Bohemia, Czech Republic. They occur as anhedral grains, up to 300 μm in size, in a calcite gangue, associated with clausthalite, cadmoselite, hakite-(Hg) [for hakite-(Cd)], berzelianite, bukovite, bytízite, crookesite, chaméanite, eskebornite, příbramite, the not yet approved giraudite-(Hg) and giraudite-(Cu), hakite-(Hg), umangite, chalcopyrite, tetrahedrite-(Zn) and a new Cu–As selenide [for hakite-(Fe) and -(Zn)]. The three new species are black, with a metallic lustre. Mohs hardness is ca. 3½–4; calculated density is 6.019 (Hak-Cd), 6.011 (Hak-Fe) and 6.081 g.cm–3 (Hak-Zn). In reflected light, they are isotropic, pale grey with bluish (Hak-Cd) or brownish (Hak-Fe and Hak-Zn) shades. Empirical formulae of hakite-(Cd), hakite-(Fe), and hakite-(Zn) are Cu9.71Ag0.24Cd1.51Hg0.43Zn0.03(Sb3.94As0.13)Σ4.07Se11.35S1.57, Cu10.11Ag0.18Fe0.81Zn0.50Hg0.26(Sb3.72As0.41)Σ4.13Se12.65S0.12, and Cu10.03Ag0.24Zn0.61Fe0.53Hg0.45(Sb3.55As0.60)Σ4.15Se12.82S0.08, respectively. These formulae correspond to the end-member formulae Cu6(Cu4Cd2)Sb4Se13 (Hak-Cd), Cu6(Cu4Fe2)Sb4Se13 (Hak-Fe), and Cu6(Cu4Zn2)Sb4Se13 (Hak-Zn). All these new members of the hakite series are cubic, I$\bar{4}$3m, Z = 2, with unit-cell parameters a = 10.8860(6) Å, V = 1290.0(2) Å3 (Hak-Cd); a = 10.7983(4) Å, V = 1259.12(14) Å3 (Hak-Fe); and a = 10.8116(14) Å, V = 1263.8(5) Å3 (Hak-Zn). These species are isotypic with the other members of the tetrahedrite group, and their crystal structures have been refined on the basis of single-crystal X-ray diffraction data down to R1 values of 0.0230 (Hak-Cd), 0.0254 (Hak-Fe), and 0.0302 (Hak-Zn). These structural data allow us to describe the S-to-Se partitioning in hakite-series minerals and to understand the mechanisms avoiding too short Me–Se distances in these selenides.

In this communication, we present a brief response to Lykova et al. (2024) who, in a paper in volume 88 https://doi.org/10.1180/mgm.2024.1 (this journal), describe the occurrence of the new mineral natromelansonite, Na3Zr(Si7AlO19)⋅4–5H2O, and provide commentary on the related species, melansonite (Na,□)□2KZrSi8O19⋅5H2O. The comments in question revolve primarily around the roles and abundances of Al and Na in both minerals, and how their incorporation is best represented in their idealised formulae.

Lykova et al. (2024) state that Al is an essential component of both melansonite and natromelansonite and should thus be reflected in the ideal formulae. With respect to Na, they propose that the ideal formula of melansonite contains two Na apfu rather than one, as was presented in our initial definition of the mineral.

We reiterate there is no unequivocal evidence that Al is an essential component of melansonite, occupying a unique crystallographic site, but rather, it only substitutes for Si. Secondly, though the true Na content of melansonite is probably higher than were originally reported (this being simply explained by the thin nature of the crystals analysed and the volatility of Na under the electron beam), it cannot reconcile the doubling of the Na apfu for melansonite, as was suggested by Lykova et al. (2024).

Organic acids are commonly found in soils and sediments, playing an important role in the alteration and weathering of minerals and influencing a series of geochemical processes such as soil fertility, metal cycling and pollutant migration. In order to better comprehend the reaction mechanisms of different layered silicate minerals with organic acids, three minerals with various structure types, namely montmorillonite, kaolinite and muscovite, were investigated in this work. In particular, the effects of interfacial reactions with oxalic acid on the crystal structure, chemical composition, morphology and specific surface area of minerals were compared. The composition and structure of montmorillonite, kaolinite and muscovite during the interfacial reaction with oxalic acid were characterised using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) methods. It was shown that Si4+ and Al3+ were dissolved gradually during the interfacial reactions and that the changes in the properties of minerals depended on structural characteristics. After 300 days of the interfacial reactions with oxalic acid, the dissolution percentages of Si4+ and Al3+ in montmorillonite, kaolinite and muscovite were 12.7%, 8.4%, 3.8% and 62.1%, 30.7%, 6.1%, respectively. Moreover, the lamellar morphology of montmorillonite was destroyed upon the interfacial reaction with oxalic acid, and irregular particles with sizes of ~100–500 nm were formed on the surface. The diameter of kaolinite flake particles decreased from 400–1500 nm to 50–400 nm, and the surface of rod-shaped particles was ruptured. The small particles disappeared from the muscovite surface, and the initially sharp edges became blunted. The specific surface area and the total pore volume of montmorillonite and kaolinite increased after the interfacial reaction with oxalic acid, whereas the opposite results were obtained for muscovite. The differential dissolution of the minerals during their interfacial reaction with oxalic acid was mainly related to the differences between cation occupancies, structural types, chemical bond strengths and specific surface areas.

Sulfosalt assemblages in a specimen from the Boliden Au–Cu–(As) deposit in northern Sweden, comprise micrometre to nanometre scale intergrowths of Se-rich izoklakeite and tintinaite with average formulae and calculated homologue number (N) given as: (Cu1.88Fe0.18)2.06(Pb22.92Ag1.47Cd0.01Zn0.01)24.41(Sb13.12Bi8.69)21.8(S50.19Se6.43Te0.12)56.73, N = 3.83, and (Cu1.31Fe0.74)2.05(Pb10.58Ag0.18Cd0.05Zn0.02)10.83(Sb10.2Bi5.23)15.43(S32.22Se2.46)34.7, N = 2.05, respectively. Tintinaite coexists with (Bi, Se)-rich jamesonite. High-angle annular dark field scanning transmission electron microscopy (HAADF STEM) imaging reveals chessboard structures comprising PbS and SnS modules with the number of atoms in the octahedral (M) sites counted as: n1 = 18 and n2 = 8 for tintinaite and n1 = 30 and n2 = 16 for izoklakeite. The homologue number can be calculated using the formula: N = (n1/6)–1 and N = n2/4 for PbS and SnS modules giving NTti = 2 and NIz = 4. A new N = 3 homologue, defined by n = 12 and n = 24 SnS and PbS modules, respectively, is identified as single or double units within areas with intergrowths between kobellite and izoklakeite. HAADF STEM imaging also reveals features attributable to lone electron pair micelles within the Sb-rich kobellite homologues. Atomic-resolution EDS STEM chemical mapping of Pb–Bi–Sb-sulfosalts shows a correlation with crystal structural modularity. The maps also highlight sites in the SnS modules of tintinaite in which Sb > Bi. Coherent nanoscale intergrowths between tintinaite and izoklakeite define jigsaw patterns evolving from chessboard structures and are considered to have formed during co-crystallisation of the two phases. Displacement textures and crosscutting veinlets (a few nm in width) are interpreted as evidence for superimposed syn-metamorphic deformation and are associated with the redistribution of Bi and Se. Imaging and mapping using HAADF STEM techniques is well suited to characterisation of Pb–Sb–Bi-sulfosalt phases, offering largely untapped potential to unravel the evolution of chessboard structures with applications across mineralogy but also extending into allied fields.

The new mineral theuerdankite, ideally Ag3AsO4, was found in the Alter Theuerdank Mine, Beerberg, St. Andreasberg, Goslar District, Lower Saxony, Germany. Theuerdankite occurs as aggregates of anhedral grains up to 3 mm in size, growing in cavities of strongly supergene-weathered material consisting of native silver and chlorargyrite (but with calcite present). It is dark violet, changing to reddish and black when exposed to the air and light. It has a grey to violet grey streak; when readily fresh, its streak is brownish-red. The Mohs hardness is ~2. It is brittle with no observable cleavage or parting and with a conchoidal fracture. The calculated density is 6.620 g⋅cm–3. In reflected light, theuerdankite is dark grey with a pinkish tint, with no observable bireflectance, pleochroism, or anisotropy. It shows dark red internal reflections. The reflectance values for wavelengths recommended by the Commission on Ore Mineralogy of the International Mineralogical Association are (R, %): 13.3 (470 nm), 12.8 (546 nm), 12.7 (589 nm) and 12.5 (650 nm). The empirical formula (based on 4 apfu) is Ag3.00As1.00O4. Theuerdankite is cubic, space group P$\bar{4}$3n, a = 6.144(2) Å, V = 231.93(13) Å3 and Z = 2. The six strongest powder X-ray diffraction lines are [dobs in Å, (I) hkl]: 3.0736, (22) 200; 2.7502, (100) 210; 2.5106, (55) 211; 1.7050, (36) 320; 1.6249, (44) 321; and 1.3412, (17) 421. The crystal structure of theuerdankite (R1 = 1.69% for 519 reflections having I > 3σ(I)), is isotypic to those of synthetic Ag3AsO4 and Ag3PO4. The Gram–Charlier development describing the higher-order tensors representing the atomic displacement parameters of the silver atom was implemented, documenting that silver tends to behave anharmonically in the theuerdankite structure at room temperature.

Sperlingite, (H2O)K(Mn2+Fe3+)(Al2Ti)(PO4)4[O(OH)][(H2O)9(OH)]⋅4H2O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in corrosion pits of altered zwieselite, in association with columbite, hopeite, leucophosphite, mitridatite, scholzite, orange–brown zincoberaunite sprays and tiny green crystals of zincolibethenite. Sperlingite forms colourless prisms with pyramidal terminations, which are predominantly only 5 to 20 μm in size, rarely to 60 μm and frequently are multiply intergrown and are overgrown with smaller crystals. The crystals are flattened on {010} and slightly elongated along [100] with forms {010}, {001} and {111}. Twinning occurs by rotation about c. The calculated density is 2.40 g⋅cm–3. Optically, sperlingite crystals are biaxial (+), α = 1.600(est), β = 1.615(5), γ = 1.635(5) (white light) and 2V (calc.) = 82.7°. The optical orientation is X = b, Y = c and Z = a. Neither dispersion nor pleochroism were observed. The empirical formula from electron microprobe analyses and structure refinement is A1[(H2O)0.96K0.04]Σ1.00 A2(K0.52□0.48)Σ1.00 M1(Mn2+0.60Mg0.33Zn0.29Fe3+0.77)Σ1.99 M2+M3(Al1.05Ti4+1.33Fe3+0.62)Σ3.00(PO4)4 X[F0.19(OH)0.94O0.87]Σ2.00[(H2O)9.23(OH)0.77]Σ10.00⋅3.96H2O. Sperlingite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.428(2) Å, b = 20.281(4) Å, c = 12.223(2) Å, β = 90.10(3)°, V = 2585.0(8) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.058 for 5608 reflections with I > 3σ(I). Sperlingite is the first paulkerrite-group mineral to have co-dominant divalent and trivalent cations at the M1 sites; All other reported members have Mn2+ or Mg dominant at M1. Local charge balance for Fe3+ at M1 is achieved by H2O → OH– at H2O coordinated to M1.

A rounded fragment of a multicoloured tourmaline crystal (2.5 cm diameter), collected from the secondary gem deposit of Mavuco, Alto Ligoña pegmatite district, Mozambique, has been investigated using a multi-analytical approach, with the objective of reconstructing its growth history. The sample represents a core-to-rim section, perpendicular to the c axis, of a crystal characterised by a variety of colours. These change from a black core to an intermediate zone with a series of colours, yellow, blue–green and purple, to a final dark-green prismatic overgrowth. These changes are the result of a wide variation in Fe, Mn, Ti and Cu concentrations and their redox state. The black core is characterised by enrichment in Fe and Mn, with iron present in its divalent state. The yellow zone shows a progressive depletion in Fe and its colouration is caused by Mn2+ and Mn2+-Ti4+ IVCT interactions. The progressive decrease in Mn coupled with the absence of Ti, and the lack of Fe, implies that Cu2+ acts as the only chromophore in the pale blue–green zone. The dominant colour-causing agent of the purplish zone is Mn3+, denoting a change in redox environment; however, even though the amount of Cu remains significant, its chromophore effect is obscured by Mn3+. The dark-green prismatic overgrowth, characterised by a sharp increase in Fe, Mn and also Ca, is interpreted as a late-stage partial re-opening of the geochemical system. This occurrence could potentially be related to mechanical instability of the cavity in which the crystal grew.

Fluor-rossmanite, ideally □(Al2Li)Al6(Si6O18)(BO3)3(OH)3F, is a new mineral of the tourmaline supergroup, found at the Krutaya pegmatite, Malkhan pegmatite field, Zabaykalskiy Krai, Western Siberia, Russia. It forms an intermediate zone up to 3 mm thick in a chemically heterogeneous, concentrically zoned, polychrome tourmaline crystal 3 × 2 cm in size. The new mineral is light pink, transparent with a white streak and a vitreous lustre. It is brittle, with conchoidal fracture. The Mohs hardness is 7. The Dmeas = 3.07(2) g cm–3 and Dcalc = 3.071 g cm–3. Optically, fluor-rossmanite is non-pleochroic, uniaxial (–), ω = 1.647(2) and ɛ = 1.628(2) (589 nm). The empirical formula calculated on the basis of 31 anions (O+OH+F) is: X(□0.46Na0.32Ca0.20Pb0.02)Σ1.00 Y(Al1.84Li1.05Mn0.05Fe2+0.02Ti0.02Cr0.01)Σ2.99 ZAl6.00 T(Si5.79Al0.21)Σ6.00B2.99O27 V(OH)3 W[F0.44(OH)0.20O0.36]Σ1.00. Fluor-rossmanite is trigonal, R3m; the unit-cell parameters are: a = 15.7951(3), c = 7.08646(17) Å, V = 1531.11(7) Å3 and Z = 3. The crystal structure is refined from single-crystal X-ray diffraction data [R = 0.0211 for 1178 unique reflections with I > 2σ(I)]. The new mineral is a ‘fluor-’ species belonging to the X-vacant group of the tourmaline supergroup. The closest end-member compositions of valid tourmaline species are those of rossmanite and fluor-elbaite, to which fluor-rossmanite is related by the substitutions WF– ↔ WOH– and X2□ + YAl3+ ↔ X2Na+ + YLi+, respectively.

Kvačekite is a new mineral species discovered in a sample collected from the now abandoned Bukov uranium mine, western Moravia, Czech Republic. It occurs as rare anhedral grains, up to 15 μm in size, associated with nickeltyrrellite, tyrrellite, berzelianite, hakite-(Zn), hakite-(Cd), eucairite, clausthalite, and gold in calcite gangue. In reflected light, kvačekite is white with a faint yellowish shade; bireflectance, pleochroism and anisotropy are absent. Internal reflections were not observed. Reflectance values for the four COM wavelengths for kvačekite in air [R (%) (λ in nm)] are: 54.9 (470); 53.5 (546); 52.6 (589); and 52.2 (650). The empirical formula, based on electron-microprobe analyses (EPMA), is (Ni0.95Cu0.04Co0.03)Σ1.02Sb1.00(Se0.97S0.01)Σ0.98. The ideal formula is NiSbSe, which requires (in wt.%) Ni 22.63, Sb 46.93, Se 30.44, total 100.00. Kvačekite is cubic, P213, with unit-cell parameters a = 6.09013(13) Å, V = 225.881(15) Å3 and Z = 4. The strongest reflections in the X-ray powder diffraction pattern of synthetic kvačekite [d, Å (I) hkl] are: 3.0458 (11) 200; 2.7242 (100) 201, 210; 2.4867 (71) 211; 1.8632(39) 311; 1.6277(29) 321, 312; and 1.3290 (13) 421. Given the similarity with ullmannite, NiSbS, the crystal structure was refined from the powder X-ray diffraction data starting from those atomic coordinates using the synthetic analogue of kvačekite. Its crystal structure is formed by corner-sharing [NiSb3Se3] octahedra which form a three-dimensional network. The identity of the natural kvačekite and synthetic cubic NiSbSe were confirmed by a study of their chemical composition, reflectance measurements, Raman spectroscopy and electron back-scattered diffraction (EBSD) measurements on the mineral. Kvačekite is named after Milan Kvaček (1930–1993), a prominent Czech mineralogist. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2023-095).

The impact of temperature on the migration of cations within layers of clay minerals is of profound significance for the design and practical application of materials derived from clay minerals. This study focuses on Li+ and Na+ as representative cations, together with illite (Ilt) and montmorillonite (Mnt) as representative clay minerals. The study investigates the behaviour of cation migration and occupation within clay minerals across varying temperatures. A series of samples were prepared meticulously by immersing illite and montmorillonite in Li+ and Na+ solutions, subsequently subjecting them to different temperatures (unheated, 100, 150, 200, 250 and 300°C) for 24 h. Through the use of techniques such as X-ray diffraction (XRD), cation exchange capacity (CEC), Fourier-transform infrared spectroscopy (FTIR), magic angle rotating solid nuclear magnetic resonance spectroscopy (MAS NMR), and X-ray photoelectron spectroscopy (XPS), the study discerns structural transformations in illite and montmorillonite, and tracks the migration and occupation of Li+ and Na+. The findings reveal that following heating, Na+ and Li+ do not infiltrate the lattice of illite. For montmorillonite, Na+ also does not migrate into the montmorillonite lattice, however, in contrast, Li+ does exhibit migration into this lattice. Notably, the migration and occupation of interlayer Li+ within montmorillonite exhibit discernible temperature dependence. Specifically, upon reaching 150°C, interlayer Li+ migrate to ditrigonal cavities within the tetrahedral layers. As the temperature elevates to 200°C, Li+ further permeate vacant octahedral sites through the ditrigonal cavities, culminating in the formation of a localised trioctahedral structure.

The ancylite supergroup has been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association, with the general crystal chemical formula (M3+xM2+2–x)(CO3)2[(OH)x⋅(2–x)H2O] (1 ≤ x ≤ 2, Z = 2). The ancylite supergroup can be divided into two groups defined by different proportions of the M cation and hydroxyl anion and/or water molecule: the ancylite group is defined for 1 ≤ x ≤ 1.5; the kozoite group is defined for 1.5 < x ≤ 2. The ancylite supergroup minerals are orthorhombic with space group Pmcn, or monoclinic with space group Pm11, and have a crystal structure with species-defining trivalent and divalent M cations (M = La3+, Ce3+, Nd3+, Ca2+, Sr2+ and Pb2+) which centre ten-vertex polyhedra formed by oxygen atoms at three independent O sites. Two vertices of the triangular (CO3)2– anion are oxygen atoms, whereas the third one, O(3), is statistically filled with (OH)– groups and H2O molecules. The triangular faces of three oxygen atoms of MO10 coordination polyhedra join the chains of this ten-vertex polyhedron, which is extended along the c axis. The (CO3) triangles connect chains in three dimensions. To date, eight valid mineral species with M2+ = Sr2+, Ca2+ and Pb2+ belong to the ancylite group [ancylite-(La), ancylite-(Ce), calcioancylite-(La), calcioancylite-(Ce), calcioancylite-(Nd), gysinite-(La), gysinite-(Ce) and gysinite-(Nd)]. Two hydroxyl carbonates with only rare earth elements as species-defining cations, kozoite-(La) and kozoite-(Nd) are members of the kozoite group.

Valsassina (Lombardy, Northern Italy) is located in the Lombard Southern Alps and is characterised by the presence of a metamorphic basement, by a major late Variscan intrusive complex and by Carboniferous–Permian volcano-sedimentary cover units. These rocks host a pervasive system of inadequately studied mineralised veins. These veins are characterised by base metal (Pb, Zn, Cu and Fe) and complex polymetallic assemblages.

In this study, we have investigated the ore textures, mineral compositions of sulfides and sulfosalts (by EMPA–WDS and LA–ICP–MS analyses), and stable isotopes (C and O) in carbonate gangue minerals of various mineralised veins to determine the conditions of deposition of these ore deposits. Two different vein families can be recognised in Valsassina: NNW–SSE veins characterised by a complex polymetallic sulfide–sulfosalt assemblage, also with Ni–Co–Fe arsenides and other Ag–Bi-bearing minerals; and NE–SW veins with a simpler, base metal sulfide assemblage. The Ni–Co-bearing NNW–SSE veins have some distinctive features of the ‘five-element vein’ type deposits, with the Ni–Co–Fe arsenide ore stage pre-dating a sulfide-tetrahedrite-dominated ore stage. LA–ICP–MS data for pyrite and sphalerite, and stable isotopic compositions (C and O) of the carbonate gangue minerals, show no clear differences between the two families of veins, which are probably linked genetically. The isotopic compositions of the Valsassina vein carbonates are closely comparable with the signature of several major five-element ore districts. Preliminary temperature estimates for the Valsassina vein systems were based on the sphalerite composition, applying the GGIMFis geothermometer. The estimated temperatures for the sulfide-dominated ore stage post-dating the Ni–Co minerals precipitation range between 100 and 250°C. The crosscutting relationships, observed for all the veins with the host rocks, suggest a possible late to post Variscan (late Permian) age, making these vein systems comparable with other late–post Variscan polyphase hydrothermal events affecting large sectors of the Southern Alpine domain.