The diffusive exchange of dissolved material between fluid flowing in a fracture and the enclosing wallrocks (rock matrix diffusion) has been proposed as a mechanism by which radionuclides derived from a radioactive waste repository may be removed from groundwater and incorporated into the geosphere. To test the effectiveness of diffusive exchange in igneous and metamorphic rocks, we have carried out an investigation of veins formed at low temperatures (<100°C), comparing the oxygen isotopic composition of vein calcite with that of secondary calcite in the wallrocks. Two examples of veins from the Borrowdale Volcanic Group, Cumbria, and one from the Mountsorrel Granodiorite, Leicestershire, UK, have remarkably similar vein calcite compositions, ca. +20‰(SMOW) or greater, substantially heavier than the probable compositions of the host rocks, and these vein calcite compositions are inferred to reflect the infiltrating fluid and the temperature of vein formation. Calcites from the wallrocks are similar to those in veins, with little evidence for exchange with the wallrocks. The results support existing models for this type of vein which suggest low-temperature growth from formation brines originally linked to Permian or Triassic evaporites. The results are consistent with flow through fractures being attenuated through a damage zone adjacent to the fracture and provide no evidence of diffusional exchange with pore waters from wallrocks.

The new mineral zincorietveldite (IMA2022-070), Zn(UO2)(SO4)2(H2O)5, was found in the Blue Lizard mine, San Juan County, Utah, USA, where it occurs as yellow to orange–yellow blades in a secondary assemblage with bobcookite, coquimbite, halotrichite, libbyite, metavoltine, rhomboclase, römerite, tamarugite and voltaite. The streak is very pale yellow. Crystals are transparent with vitreous lustre. The tenacity is brittle, the Mohs hardness is ~2½ and the fracture is curved. Cleavage is excellent on {010}, good on {100} and fair on {001}. The mineral is easily soluble in H2O and has a calculated density of 3.376 g⋅cm–3. The mineral is optically biaxial (+) with α = 1.568(2), β = 1.577(2) and γ = 1.595(2); 2V = 70(1)°. Electron microprobe analyses provided (Zn0.720Mg0.109Fe0.091Mn0.046Co0.035)Σ1.00(UO2)(SO4)2(H2O)5. Zincorietveldite is orthorhombic, Pmn21, a = 12.8712(9), b = 8.3148(4), c = 11.2959(4) Å, V = 1208.90(11) Å3 and Z = 4. Zincorietveldite is the Zn analogue of rietveldite. The structural unit is a uranyl-sulfate chain that is also found in the structures of bobcookite, oldsite, oppenheimerite and svornostite.

A new mineral species, mikenewite (IMA2022-102), ideally Mn2+(S4+O3)⋅3H2O, has been discovered from the San Judas Chimney, Ojuela mine, Mapimí, Durango, Mexico. It occurs as spheres of platy crystals. Associated minerals include goethite, cryptomelane, adamite and lotharmeyerite. Mikenewite is yellowish in transmitted light, transparent with a white streak and vitreous lustre. It is brittle and has a Mohs hardness of 2½–3. Cleavage is perfect on {101}. The measured and calculated densities are 2.48(5) and 2.467 g/cm3, respectively. Optically, mikenewite is biaxial (+), with α = 1.606(5), β = 1.614(5), γ = 1.627(1) (white light), 2V(meas.) = 69(3)° and 2V(calc.) = 77°. An electron microprobe analysis yielded an empirical formula (based on 6 O apfu) of (Mn0.86Zn0.12Fe0.04Ca0.02)Σ1.04(S0.98O3)⋅3H2O, which can be simplified to (Mn,Zn,Fe)(SO3)⋅3H2O.

Mikenewite is the natural analogue of synthetic α-Mn2+(S4+O3)⋅3H2O, as well as the Mn-analogue of albertiniite, Fe2+(S4+O3)⋅3H2O. It is monoclinic, with space group P21/n and unit-cell parameters a = 6.6390(3), b = 8.8895(4), c = 8.7900(4) Å, β = 96.095(2)°, V = 515.83(4) Å3 and Z = 4. The crystal structure of mikenewite is characterised by each Mn atom coordinated octahedrally by six O atoms, three from different sulfite O atoms and three from H2O molecules. Each S4+O3 group is bonded to three Mn atoms, resulting in a sheet parallel to (101) with the sheet composition of Mn2+(S4+O3)⋅3H2O. Such sheets, stacked along [10$\bar{1}$], are joined together by hydrogen bonds, accounting for the perfect cleavage of the mineral. Mikenewite is dimorphous with orthorhombic Pnma gravegliaite, as albertiniite is with fleisstalite. Its discovery from the Ojuela mine, which is particularly rich in Zn, implies the possibility of finding Zn-bearing sulfites there as well.

The thermal behaviour of fedorite from the Murun massif, Russia, has been investigated by means of electron probe microanalysis (EPMA), differential thermal analysis (DTA), thermogravimetry (TG), in situ high-temperature single-crystal X-ray diffraction (HT-SCXRD), ex situ high-temperature Fourier-transform infrared spectroscopy (HT-FTIR). The empirical chemical formula of the sample of fedorite studied is: (Na1.56K0.72Sr0.12)Σ2.40(Ca4.42Na2.54Mn0.02Fe0.01Mg0.01)Σ7.00(Si15.98Al0.02)Σ16.00(F1.92Cl0.09)Σ2.01(O37.93OH0.07)Σ38.00⋅2.8H2O. The TG curve provides a total mass decrease of ~5.5%, associated with dehydration and defluorination processes from 25 to 1050°C. Fedorite crystallises in space group P$\bar{1}$ and has: a = 9.6458(2), b = 9.6521(2), c = 12.6202(4) Å, α = 102.458(2), β = 96.2250(10), γ = 119.9020(10)° and cell volume, V = 961.69(5) Å3. The HT-SCXRD was carried out in air in the 25–600°C range. Overall, a continuous expansion of the unit-cell volume was observed although the c cell dimension slightly decreases in the explored temperature range. Structure refinements indicated that the mineral undergoes a dehydration process with the loss of most of the interlayer H2O from 25 to 300°C. The HT-FTIR spectra confirmed that fedorite progressively dehydrates until 700°C.

Calcioancylite-(La), ideally (La,Ca)2(CO3)2(OH,H2O)2, has been discovered from nepheline syenite of the Gejiu alkaline complex in the Honghe Hani and Yi Autonomous Prefecture, Yunnan Province, China. The mineral occurs as aggregates of subhedral grains, and the size of single crystals varies between 5–20 μm. Calcioancylite-(La) is colourless to pale pinkish grey and has transparent to translucent lustre. It is brittle with a Mohs hardness of 4. The calculated density is 4.324 g/cm3. The mineral is biaxial (−), with α =1.662, β = 1.730, γ = 1.771, 2Vmeas. = 70°(1) and 2Vcalc. = 73°. Electron microprobe analysis for holotype material yielded an empirical formula of (La0.58Ce0.55Pr0.14Nd0.10Ca0.39Sr0.20K0.04)Σ2.00(CO3)2[(OH)1.25F0.06⋅0.69H2O]Σ2.00. Calcioancylite-(La) is orthorhombic, with space group Pmcn, a = 5.0253(3) Å, b = 8.5152(6) Å, c = 7.2717(6) Å, V = 311.17(4) Å3 and Z = 2. By using single-crystal X-ray diffraction, the crystal structure has been determined and refined to a final R1 = 0.0652 on the basis of 347 independent reflections (I > 2σ). The seven strongest powder X-ray diffraction lines [d in Å (I) (hkl)] are: 2.334 (100) (013), 2.970 (80) (121), 4.334 (75) (110), 3.678 (68) (111), 2.517 (55) (200), 2.647 (47) (031) and 2.077 (44) (221). Calcioancylite-(La) is the La-analogue of calcioancylite-(Ce) and is a new member of ancylite-group minerals. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2021-090).

The chemistry and the crystal structure of the recently described mineral argentopolybasite are critically discussed based on the study of two new occurrences of the mineral: Gowganda, Timiskaming District, Ontario, Canada and IXL Mine, Silver Mountain mining district, Alpine County, California.

The crystal structure of argentopolybasite can be described as the sequence, along the c axis, of two alternating layers: a [Ag6Sb2S7]2– A layer and a [Ag10S4]2+ B layer. In the B layer there are linearly-coordinated metal positions (B sites), which are usually occupied by copper in all members of the pearceite–polybasite group, resulting in a B-layer composition [Ag9CuS4]2+. In argentopolybasite, however, Ag fills all the metal sites in both A and B layers. By means of a multi-regression analysis on 67 samples of the pearceite–polybasite group, which were studied by electron microprobe and single-crystal X-ray diffraction, the effect of Ag, Sb and Se on the B sites of the B layer was modelled. Although the nomenclature rules for these minerals are based on chemical data only, we think this approach is useful to evaluate the goodness of the refinement of the structure (Ag/Cu disorder) and thus fundamental to discriminate different members of the pearceite–polybasite group.

Monazite-(Gd), ideally GdPO4, is a new mineral of the monazite group. It was discovered near Prakovce-Zimná Voda, ~23 km WNW of Košice, Western Carpathians, Slovakia. It forms anhedral domains (≤100 μm, mostly 10–50 μm in size), in close association with monazite-(Sm), Gd-bearing xenotime-(Y), Gd-bearing hingganite-(Y), fluorapatite and uraninite. All these minerals are hosted in a REE–U–Au quartz–muscovite vein, hosted in phyllites in an exocontact to granites. The density calculated using the average empirical formula and unit-cell parameters is 5.55 g/cm3. The average chemical composition measured by means of electron microprobe is as follows (wt.%): P2O5 29.68, As2O5 0.15, SiO2 0.07, ThO2 0.01, UO2 0.04, Y2O3 1.30, La2O3 3.19, Ce2O3 6.93, Pr2O3 1.12, Nd2O3 10.56, Sm2O3 17.36, Eu2O3 1.49, Gd2O3 22.84, Tb2O3 1.57, Dy2O3 2.27, CaO 0.21, total 99.67. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.30Sm0.24Nd0.15Ce0.10La0.05Dy0.03Y0.03Tb0.02Eu0.02Pr0.02Ca0.01)0.98P1.01O4. The ideal formula is GdPO4. The monazite-type structure has been confirmed by micro-Raman spectroscopy and selected-area electron diffraction. Monazite-(Gd) is monoclinic, space group P21/n, a = 6.703(1) Å, b = 6.914(1) Å, c = 6.383(1) Å, β = 103.8(1)°, V = 287.3(1) Å3 and Z = 4. The middle REE enrichment of monazite-(Gd) is shared with the associated Gd-bearing xenotime-(Y) to ‘xenotime-(Gd)’ and Gd-bearing hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing mineral assemblage is a product of selective complexing and enrichment in middle REE in low-temperature hydrothermal fluids by alteration of primary uraninite, brannerite and fluorapatite on a micro-scale. The new mineral is named as an analogue of monazite-(La), monazite-(Ce), monazite-(Nd) and monazite-(Sm) but with Gd dominant among the REE.

Monazites are one of the most interesting groups of accessory mineral components of crystalline rocks due to the information on geochemical evolution of the crystallisation environment coded in their chemical compositions, in addition to comprising one of the most valuable objects for geochronology studies. This paper presents monazite-(Sm) and monazite-(Nd) from the Blue Beryl Dyke of the Julianna system of rare-element pegmatites at Piława Górna, Lower Silesia, Poland. These monazites are unique due to their unusually high Sm and Nd contents, reaching 33.22 wt.% Sm2O3 and 34.12 wt.% Nd2O3, respectively. We consider the most significant factors of the enrichment in Sm and Nd to be the occurrence of highly fractionated pegmatite-forming melts during the final stages of solidification and associated hydrothermal fluids that were strongly enriched in rare earth element REE–Cl and REE–F complexes. Local disequilibria allowed for the rapid growth of accessory phases under supercooling conditions associated with the scavenging of selected elements, leading to their local depletion, which was not balanced by diffusion processes. As a consequence, the depletion of light rare earth elements (LREE) led to the incorporation of available middle rare earth elements (MREE, Sm–Dy) in the case of Sm and Nd, which could occupy an acceptable structural position in minerals of the monazite group.

A new mineral species, holubite, ideally Ag3Pb6(Sb8Bi3)Σ11S24, has been found at Kutná Hora ore district, Czech Republic. The mineral is associated with other lillianite homologues (gustavite, terrywallaceite, vikingite and treasurite) most frequently as grain aggregates and replacement rims of earlier Ag–Pb–Bi minerals, growing together in aggregates up to 200 × 50 μm. It typically occurs in a close association with Ag,Bi-bearing galena and terrywallaceite. Holubite is opaque, steel-grey in colour and has a metallic lustre, the calculated density is 5.899 g/cm3. In reflected light holubite is greyish white and bireflectance and pleochroism are weak with grey tints. Anisotropy is weak to medium with grey to bluish-grey rotation tints. Internal reflections were not observed. Electron microprobe analyses yielded an empirical formula, based on 44 atoms per formula unit (apfu) of (Ag3.03Cu0.03)Σ3.06(Pb6.19Fe0.02Cd0.01)Σ6.22(Sb7.71Bi2.90)Σ10.61S24.12. Its unit-cell parameters are: a = 19.374(4), b = 13.201(3), c = 8.651(2) Å, β = 90.112(18)°, V = 2212.5(9) Å3, space group P21/n and Z = 2. Holubite is a new member of the andorite branch of the lillianite homologous series with N = 4. The structure of holubite contains two Pb sites with a trigonal prismatic coordination, eight distinct octahedral sites, of which one is a mixed (Bi,Ag) site and one is a mixed (Sb,Pb) site, and twelve anion sites. Holubite is defined as a lillianite homologue with the three following requirements: N = 4, L% [Ag+ + (Bi3+,Sb3+) ↔ 2 Pb2+ substitution] ≈ 70% and approximately one quarter to one third at.% of antimony is replaced by bismuth [Bi/(Bi+Sb) ≈ 0.26–34]. The new mineral has been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2022-112) and named after Milan Holub, a key Czech geologist and specialist in the Kutná Hora ore district.

The new mineral tennantite-(Ni), Cu6(Cu4Ni2)As4S13, has been discovered from the Luobusa Chromitite, Tibet, southwestern China. Tennantite-(Ni) occurs as anhedral grains ranging from 2 to 20 μm in size. In reflected light microscopy, tennantite-(Ni) is isotropic and appears yellow-greenish grey. Reflectance data for Commission on Ore Mineralogy wavelengths in air for tennantite-(Ni) are: 31.0 (470 nm), 29.6 (546 nm), 29.6 (589 nm) and 29.3 (650 nm). Electron microprobe analysis for holotype material gave the empirical formula (on basis of total cations = 16 apfu): M(2)Cu6 M(1)[Cu4.00(Ni0.97Cu0.53Fe0.50)Σ2.00]Σ6.00X(3)(As2.94Sb1.06)Σ4S12.77. Tennantite-(Ni) is cubic, with space group I$\bar{ 4}$3m (#217), a =10.2957(9) Å, V = 1091.4(3) Å3 and Z = 2. By using single-crystal X-ray diffraction, the crystal structure has been determined and refined to a final R1 = 0.0423 on the basis of 163 independent reflections [Fo > 4σ (Fo)]. The calculated seven strongest powder X-ray diffraction lines [d in Å (I) (hkl)] are: 2.972 (100) (222), 1.820 (83) (440), 2.574 (28) (400), 1.552 (18) (622), 3.640 (10) (220), 1.880 (10) (521) and 1.287 (7) (800). Tennantite-(Ni) is isostructural with other tetrahedrite-group minerals, and nickel is hosted at the tetrahedrally coordinated M(1) site, along with Cu and minor Fe. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2021-018).

Vanadium is the dominant trace element and chromophore in tanzanite, the most valued gemmological variety of zoisite. The structure of zoisite–tanzanite was obtained by structural refinement to assess the vanadium location in the zoisite structure. However, the small V content in tanzanite evidenced by electron microprobe and laser ablation inductively coupled plasma mass spectrometry limits the exact determination of the V position in the zoisite structure. Structural refinement revealed that the average bond length of the less distorted M1,2O6 octahedron is below 1.90 Å, and M3O6 has slightly longer bonds with an average of ca. 1.96 Å. The M1,2 site is slightly overbonded with a bond-valence sum (BVS) of 3.03 vu, whereas M3 is slightly underbonded (BVS = 2.78 vu). Optical absorption spectra revealed that most V is trivalent, but a small portion is probably in a four-valent state. Therefore, crystal field Superposition Model and Bond-Valence Model calculations were applied based on several necessary assumptions: (1) V occupies octahedral sites; and (2) it can occur in two oxidation states, V3+ or V4+. Crystal field Superposition Model calculations from the optical spectra indicated that V3+ prefers occupying the M1,2 site; the preference of V4+ from the present data was impossible to determine. Bond-Valence Model calculations revealed no unambiguous preference for V3+, although simple bond-length calculation suggests the preference of the M3 site. However, it is quite straightforward that the M1,2 site is better suitable for V4+. If the possible octahedral distortion is considered, the M1,2O6 octahedron is subject to a smaller change in distortion if occupied by V3+ than the M3O6 octahedron. Consequently, considering the results of both the crystal field Superposition Model and Bond-Valence Model calculations, we assume that both V3+ and V4+ prefer the M1,2 site.

Dongchuanite, ideally Pb4VIZnIVZn2(PO4)2(PO4)2(OH)2, is a new phosphate mineral with a new type of structure. It was found at the Dongchuan copper mine, Yunnan Province, People's Republic of China. Dongchuanite generally occurs as spherical aggregates with microscopic lamellar crystals, characterised by a turquoise–greenish blue colour. It is transparent, with a colourless streak and has a vitreous lustre without fluorescence. It is brittle with a Mohs hardness of 2–2½, and has good parallel cleavage to {011}, with insignificant parting and even fracture. According to the empirical formula and cell volume, it has a calculated density of 6.06 g/cm3. It easily dissolves in acid without gas being emitted. The mineral is biaxial (–), calculated n = 1.90 and maximum birefringence: δ = 0.010 and 2V=70°. Dispersion of the optical axes r < v is very weak. The mineral is pale blue to light blue and very weakly pleochroic in transmitted light. Dongchuanite crystallises in the triclinic space group P$\bar{1}$, with unit-cell parameters a = 4.7620(10) Å, b = 8.5070(20) Å, c = 10.3641(19) Å, α = 97.110(17)°, β = 101.465(17)°, γ = 92.273(18)°, V = 407.44(15) Å3 and Z = 1. The eight strongest reflections in the powder X-ray diffraction pattern [dobs, Å (I/I0) (hkl)] are: 3.442 (100) ($\bar{1}$12), 3.035 (50) (120), 4.652 (45) (100), 2.923 (40) ($\bar{1}\bar{1}$3), 2.384 (35) ($\bar{2}$01), 3.130 (30) ($\bar{1}$21), 2.811 (30) (030) and 2.316 (18) (032). The crystal structure (solved and refined from single-crystal X-ray diffraction data, R1 = 0.07) is a new layered structure consisting of corner-sharing tetrahedrons and octahedrons, where [PO4] tetrahedra and [ZnO4] tetrahedra share corners to form a double chain, and the another [PO4] tetrahedra is connected by corner-sharing with a [ZnO4(OH)2] octahedra to form a tetrahedral–octahedral chain, extending along the a-axis direction. The two types of chains are connected by corner-sharing between [ZnO4] and [PO4] tetrahedra forming a wrinkled layer parallel to (011). The Pb atoms occupy two independent sites between the wrinkled layers, both of which have typical lopsided coordination of Pb2+ with stereoactive 6s2 lone-pair electrons.

Corundum with inclusions of enigmatic super-reduced minerals was found in mineral separates received as a result of alluvial sediment exploration near Mt Carmel, Israel by the Shefa Yamim Company. This corundum, registered as ‘Carmel sapphireTM’, has been an object of numerous publications by W. Griffin's scientific team, in which they propose a questionable hypothesis of sapphire formation at the crust–mantle boundary with the participation of CH4+H2 fluids. Typically the Carmel sapphire is in small fragments of breccia with white cement, which in the opinion of Griffin et al. is a carbonate-cemented volcanic ash. Our investigation of the ‘white breccia’ showed that it consists of unsorted angular fragments of Carmel sapphire from ~1 μm to 7 mm in size cemented by aluminium hydroxides (bauxite) and is a waste product of the fused alumina process, i.e. it has an anthropogenic origin. Phases typical for slags of fused alumina production and metallurgical slags were identified in the ‘white breccia’. Carmel sapphire has numerous microscopic spherical inclusions of Si–Fe alloy indicating that the removal of Si and Fe from the corundum melt occurred at a temperature >2000°С. Osbornite, TiN, from Carmel sapphire has a chemical zonation characteristic of osbornite from fused alumina with enrichment of central zones in carbon. Comparison of the growth heterogeneity of Carmel sapphire and ‘electrocorundum’ indicates that the crystallisation of the corundum melt proceeded in a similar way. Unfortunately, in the case of Carmel sapphire from the Carmel locality, the contamination of geological samples with anthropogenic material has led to popularisation of biased views.