We report the crystal structures of eight new synthetic multinary Rb–Cu sulfates representing four new structure types: δ-Rb2Cu(SO4)2, γ-RbNaCu(SO4)2, γ-RbKCu(SO4)2, Rb2Cu2(SO4)3, Rb2Cu2(SO4)3(H2O), β-Rb2Cu(SO4)Cl2, β-Rb4Cu4O2(SO4)4⋅(Cu0.83Rb0.17Cl) and Rb2Cu5O(SO4)5. The determination of their crystal structures significantly expands the family of anhydrous copper sulfates. Some of the anhydrous rubidium copper sulfates obtained turned out to be isostructural to known compounds and minerals. Rb2Cu5O(SO4)5 is isostructural to cesiodymite, CsKCu5O(SO4)5 and cryptochalcite, K2Cu5O(SO4)5. Rb2Cu2(SO4)3 also shows an example of crystallisation in the already known structure type first observed for synthetic K2Cu2(SO4)3. ‘Hydrolangbeinite’, Rb2Cu2(SO4)3(H2O), was formed as a result of a minor hydration of the initial mixture of reagents.

The minerals and synthetic framework compounds of the A2Cu(SO4)2 series demonstrate a vivid example of morphotropism with the formation of structural types depending on the size of the cations residing in the cavities of the [Cu(SO4)2]2– open framework. To date, five types (α, β, γ, δ and ε) can be distinguished. We propose to call this series of compounds ‘saranchinaite-type’, as the stoichiometry A2Cu(SO4)2 was first encountered during the discovery and description of saranchinaite, Na2Cu(SO4)2.

The discovery of β-Rb2Cu(SO4)Cl2, a new monoclinic polymorph of chlorothionite, seems to be of particular interest considering the recently discovered interesting magnetic properties of synthetic K2Cu(SO4)X2 (X = Cl and Br) and Na2Cu(SO4)Cl2.

In these new structural architectures, a number of features have been revealed that were seldom observed previously. The first is the bidentate coordination of the sulfate tetrahedron via edge-sharing with the Cu2+-centred coordination polyhedron. Until recently, such coordination was known only for the chlorothionite structure. The second is formation of ‘high-coordinate’ CuO7 polyhedra. The structures of the new compounds suggest that such coordination is not in fact so uncommon, at least among anhydrous alkali copper sulfates. All of the described features clearly indicate the importance of further systematic studies of anhydrous copper-sulfate systems. Their exploration, particularly of the new copper-oxide substructures with new coordination environments, is highly likely to lead to new potentially interesting magnetic properties due to the unusual arrangements of magnetically active Cu2+ cations.

In addition to experimental details on the synthesis of rubidium analogues of anhydrous potassium and sodium sulfates, this work also provides an analysis and a brief review of the geochemistry of rubidium in volcanic environments.

Pyrrhotite Fe1–xS is the main sulfide component of platinum-group element (PGE) ores and commonly contains from a few tenths to a few dozen ppm of disseminated Pt. Here we report an X-ray absorption spectroscopy investigation into the state of Pt in synthetic pyrrhotite in combination with theoretical spectra modelling. The pyrrhotite crystals were obtained by means of the salt flux technique, using a eutectic mixture of alkali metal halides as the transport media. Analysis of the chemical composition of synthesised crystals showed that an increase of the temperature and sulfur fugacity yields higher concentrations of Pt in pyrrhotite. The Pt content reached 0.6 wt.% at the maximum temperature and sulfur fugacity (t = 720°C, log $f_{{\rm S}_ 2}$ = –0.1) achieved in a Pt-saturated system. X-ray absorption near-edge structure (XANES) analysis of Pt L3-edge spectra revealed that Pt is present in pyrrhotite in the 4+ and 2+ ‘formal’ oxidation states. Theoretical modelling of XANES and interpretation of extended X-ray absorption fine structure (EXAFS) spectra showed that Pt4+ substitutes for Fe in the crystal lattice of pyrrhotite, whereas Pt2+ forms PtS-like clusters disseminated in the pyrrhotite matrix. Atoms of isomorphous Pt4+ are surrounded by 6 S atoms at a distance of 2.39 ± 0.02 Å. According to theoretical simulations using the FDMNES program, the second coordination sphere of the solid-solution Pt contains one vacancy in the Fe sublattice within the Fe-layer. The Pt2+S-like clusters can be considered as a quench product. High sulfur fugacity stabilises the solid-solution Pt and prevents the formation of the PtS-like clusters during cooling. The maximum content of the solid-solution Pt in pyrrhotite is ca. 50 times lower than in pyrite and can be approximated by a straight line in the log C(Pt) vs. 1/T plot, it increases from 1 ppm at 350°C to 3 wt.% at 900°C.

Whiteite-(MnMnMn), Mn2+Mn2+Mn2+2Al2(PO4)4(OH)2⋅8H2O, is a new whiteite-subgroup member of the jahnsite group from the Foote Lithium Company mine, Kings Mountain district, Cleveland County, North Carolina, USA. It was found in small vugs of partially oxidised pegmatite minerals on the East dump of the mine, in association with eosphorite, hureaulite, fairfieldite, mangangordonite, whiteite-(CaMnMn) and jasonsmithite. It occurs as sugary aggregates of blade-like crystals up to 0.1 mm long and as epitaxial overgrowths on whiteite-(CaMnMn). The crystals are colourless to very pale brown, with a vitreous lustre and a white streak. The blades are flattened on {001} and elongated along [010], with poor cleavage on {001}. The calculated density is 2.82 g⋅cm–3. Optically it is biaxial (–) with α = 1.599(2), β = 1.605(2), γ = 1.609(2) (white light); 2V (calc.) = 78.2°, having no observable dispersion or pleochroism, and with orientation X = b. Electron microprobe analyses and structure refinement gave the empirical formula (Mn2+0.59Ca0.38Na0.03)Σ1.00Mn1.00(Mn2+1.04Fe3+0.58Fe2+0.23Zn0.16Mg0.08)Σ2.09Al2.04(PO4)3.89(OH)3.18(H2O)7.26. Whiteite-(MnMnMn) is monoclinic, P2/a, a = 15.024(3) Å, b = 6.9470(14) Å, c = 9.999(2) Å, β = 110.71(3)°, V = 976.2(4) Å3 and Z = 2. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.057 for 2014 reflections with I > 3σ(I). Site occupancy refinements confirm the ordering of dominant Mn in the X, M1 and M2 sites of the general jahnsite-group formula XM1(M2)2(M3)2(H2O)8(OH)2(PO4)4. A review of published crystallochemical data for jahnsite-group minerals shows a consistent chemical pressure effect in these minerals, manifested as a contraction of the unit-cell parameter, a, as the mean size of the X and M1 site cations increases. This is analogous to negative thermal expansion, but with increasing cation size, rather than heating, inducing octahedral rotations that result in an anisotropic contraction of the unit cell.

Ancient metamorphic processes are recorded by the formation of metallic-Pb nanospheres in zircon, a product of internal Pb mobilisation and thermally driven concentration. Here, metallic-Pb nanospheres formed within an ore deposit are characterised for the first time using high-angle annular dark field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy element-distribution mapping. Exceptional examples from the migmatite-hosted Archean–Paleoproterozoic Challenger Au deposit (Central Gawler Craton, South Australia) support widespread metallic-Pb nanosphere formation in zircon from rocks experiencing granulite-facies metamorphism. We also report new trace-element associations found with metallic-Pb nanospheres and a new mode of occurrence, in which Sc ‘haloes’ form adjacent to metallic-Pb nanospheres within the crystalline zircon lattice. This differs to previously characterised examples of metallic-Pb nanospheres associated with amorphous Si-rich glasses and unidentified Al–Ti, or Fe-bearing phases. Multiple modes of metallic-Pb nanosphere occurrences and trace-element associations suggests multiple modes of formation, probably dependant on zircon composition and metamorphic conditions. Identification of metallic-Pb nanospheres in a growing range of geological settings further highlights the mobility of Pb in zircon and the importance of detailed, nanoscale mineral characterisation, in order to constrain accurate geochronological histories for rocks within high-temperature geological environments.

Gallium (Ga) and germanium (Ge) are technologically important critical elements. Lead blast furnace slags from Tsumeb, Namibia, comprise over two million metric tons of material that contains high levels of Ga (135–156 ppm) and Ge (128–441 ppm) in addition to significant Zn concentrations (up to 11 wt.%) and represent a potential resource for these elements. A combination of mineralogical and chemical methods (PXRD, FEG-SEM-EPMA and LA-ICP-MS) indicated different partitioning of Ga and Ge within the individual slag phases. Gallium is predominantly bound in small euhedral crystals of Zn–Fe–Al spinels (<10 μm in size), exhibiting concentrations in the range of 480–1370 ppm (up to 0.004 atoms per formula unit, apfu). Concentrations of Ga in other phases (e.g. melilite) are systematically below 90 ppm. The principal host of Ge is the silicate glass and, to a lesser extent, silicates (melilite and olivine group phases). Concentrations of Ge in glass attained a concentration of 470 ppm (EPMA), but the LA-ICP-MS analysis of glass matrix containing submicrometre spinel crystallites indicated that average Ge levels vary in the range of 113–394 ppm. In the potential extraction of Ga and Ge, the results indicate that ultrafine milling is needed to liberate the Ga- and Ge-hosting phases prior to metallurgical processing of the slag.

Hydroplumboelsmoreite (IMA21-C), (Pb,□)2(W,Fe3+)2O6(H2O), is a redefined elsmoreite-group mineral in the pyrochlore supergroup. It was found in a ‘jixianite’ cotype specimen provided by Mr. Liu Jianchang, who first found ‘jixianite’ in 1979 in the Jizhou District, Tianjin City, China. The mineral occurs as yellow to reddish brown aggregates, together with raspite and another elsmoreite-group mineral under study. Hydroplumboelsmoreite occurs in cryptocrystalline form and occasionally in octahedral microcrystalline form (under 20 μm in size). The crystals are colourless and translucent with a white streak, and the lustre is adamantine to greasy. Hydroplumboelsmoreite is isotropic, with a calculated refractive index of 2.29, a Mohs hardness of ~4½–5, and a calculated density of 7.47 g⋅cm−3. The strongest five powder X-ray diffraction lines [d in Å(I)(hkl)] are 6.070(28)(111), 3.012(100)(222), 2.603(32)(004), 1.836(35)(044) and 1.568(30)(226). The crystal structure was refined to R1 = 0.0459 using 80 unique reflections collected with MoKα radiation, and the results show that the mineral is cubic, space group Fd$\bar{3}$m, with a = 10.3377(5) Å, V = 1104.77(16) Å3 and Z = 8. Electron microprobe analyses and crystal structure refinement were used to determine the empirical formula: (Pb1.05Sr0.05Ce3+0.07Na0.01□0.82)Σ2.00(W1.32Fe3+0.67Zr0.01)Σ2.00O6[(H2O)0.43O0.19□0.38]Σ1.00. The mineral was named hydroplumboelsmoreite based on the predominance of Pb, W, and molecular H2O in the A, B and Y sites, respectively.

Armellinoite-(Ce), ideally Ca4Ce4+(AsO4)4⋅H2O, is a new mineral discovered in Fe–Mn ore in metaquartzites of the Montaldo mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as very small and rare, pale yellow to brown–yellow pseudo-octahedral translucent crystals hosted by a matrix of quartz, hematite, cryptomelane/hollandite, tilasite, muscovite, braunite and montmorillonite. The mineral is translucent, with white streak and has a resinous to vitreous lustre. It is brittle with irregular fracture and fair cleavage parallel to {110} and {100}. Estimated Mohs hardness is ~3–3.5. Calculated density is 4.29 g⋅cm–3. Armellinote-(Ce) is uniaxial (–), ω = 1.795(5), ɛ = 1.765(5) (white light), non-pleochroic and non-fluorescent. Chemical point analyses by WDS-EPMA yielded the empirical formula (based on 17 O+F anions): A(Ca3.89Th0.08Sr0.02La0.03)Σ4.02B(Ce4+0.76Nd0.13Y0.08Gd0.03Sm0.02Pr0.01Dy0.01Ho0.01)Σ1.05[(As4.00P0.01)Σ4.01O4]4⋅(H2O0.85F0.15)Σ2.00. The presence of H2O was confirmed by Raman spectroscopy. The mineral is tetragonal, I41/a, with single-crystal unit-cell parameters a = 10.749(2), c = 12.030(2) Å and V = 1390.0(6) Å3, with Z = 4. The eight strongest X-ray powder diffraction lines are [d Å (Irel; hkl)]: 7.983 (36; 101), 4.443 (23; 2̄11), 2.957 (100; 3̄12), 2.398 (14; 420), 1.875 (22; 424, 325), 1.728 (19; 3̄16), 1.612 (13; 613) and 1.475 (26; 712, 552). The crystal structure (R1 = 0.0284 for 1275 unique reflections) has isolated TO4 (T = As5+) tetrahedra that link Ca2+- or Ce4+-centred polyhedra via common oxygen ligands to form 2D blocks or double-layered (DL) structural units parallel to (001). Armellinoite-(Ce) is isostructural with pottsite, ideally (Pb3Bi)Bi(VO4)4⋅H2O, and closely related to a larger number of anhydrous synthetic compounds. The mineral is named after the mineral collector Gianluca Armellino (b. 1962), who collected the discovery sample.