Thermodynamic data are constrained by the interrelated thermodynamic equations in addition to the observational measurements and their uncertainties. The consequence is a network of thermodynamic properties that can be evaluated for their internal consistency. In this study, three fluoride minerals that can cause high fluoride concentrations in groundwaters are evaluated for their solubilities and their internal thermodynamic consistency with calorimetric, isopiestic and electrochemical measurements: fluorite, CaF2, cryolite, Na3AlF6, and villiaumite, NaF. This evaluation involves the three solids and 13 aqueous species, the free ions of Ca2+, Na+, Al3+ and F–, and the hydroxido and fluorido complexes of Al3+, and the CaF+ ion pair. For the fluorite–cryolite–villiaumite–aqueous species network, the number of components is minimal, and the solubility studies are mostly of high quality. Re-evaluations of original data using PHREEQC helps to broaden the quantitative evaluation of thermodynamic properties and to resolve apparent discrepancies. A check on this thermodynamic network shows that through a careful appraisal of the literature, a highly consistent set of values can be derived. The resultant infinite-dilution solubility-product constants at 25°C and 1 bar are: for fluorite solubility, logKsp = –10.57 ± 0.08; for cryolite solubility, logKsp = –33.9 ± 0.2; and for villiaumite solubility, logKsp = –0.4981 ± 0.003.

Tennantite-(Cu), Cu12As4S13, was approved as a new mineral species from the Layo epithermal deposit, Castilla Province, Arequipa Department, Peru, where it occurs as black metallic anhedral grains, up to 0.1 mm across, replacing enargite and associated with chalcopyrite and vinciennite. In reflected light, tennantite-(Cu) is isotropic, grey with a bluish shade. Reflectance data for the four COM wavelengths in air are [λ (nm): R (%)]: 470: 29.1; 546: 28.4; 589: 27.4; and 650: 25.0. Electron microprobe analysis for holotype material gave (in wt.% – average of 10 spot analyses): Cu 49.32(27), Fe 2.20(12), Zn 0.09(2), Sn 0.03(5), As 19.45(43), Sb 1.94(10), Te 0.02(5), S 27.75(43), total 100.80(20). On the basis of (As + Sb + Te) = 4 atoms per formula unit (apfu), the empirical formula of tennantite-(Cu) is (Cu11.27Fe0.57Zn0.02)Σ11.86(As3.77Sb0.23)Σ4.00S12.57. Tennantite-(Cu) is cubic, I$\overline 4$3m, with unit-cell parameters a = 10.1710(10) Å, V = 1052.2(2) Å3 and Z = 2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1 = 0.0178 on the basis of 263 unique reflections with Fo > 4σ(Fo) and 24 refined parameters. Tennantite-(Cu) is isotypic with other tetrahedrite-group minerals. Previous findings of tennantite-(Cu) are reported and some nomenclature issues, related to the Fe and Cu oxidation states, are discussed. At the Layo epithermal deposit, tennantite-(Cu) is the result of the replacement of enargite under decreasing $f_{{\rm S}_ 2}$ conditions.

The crystal chemistry and crystal structure of the rare earth element phosphates, monazite-(Ce), Ce(PO4), and xenotime-(Y), Y(PO4), as well as the arsenates, gasparite-(Ce), Ce(AsO4), and chernovite-(Y), Y(AsO4), from the hydrothermal quartz-bearing fissures, related to pegmatites overprinted by amphibolite facies, cropping out at Mt. Cervandone, Western Alps, Piedmont, Italy, have been investigated by means of electron microprobe analysis in wavelength dispersion mode and single-crystal X-ray diffraction. The chemical data reveal the occurrence of a full solid solution among the isostructural chernovite-(Y) and xenotime-(Y) with tetragonal symmetry, whereas a wide miscibility gap is observed for the isostructural gasparite-(Ce) and monazite-(Ce) of Mt. Cervandone, with monoclinic symmetry. A significant chemical heterogeneity has been observed for several investigated samples, especially related to the Th content, which is locally enriched in ThSiO4 grains. The analysis of the refined structural models demonstrates the significant control played by the composition of the tetrahedrally-coordinated (As,P)-bearing sites on the bulk unit-cell volume, and on the size and shape of the (REE)-coordination polyhedra.

Ferrofettelite, ideally [Ag6As2S7][Ag10FeAs2S8], is a new mineral (IMA2021-094) from the Glasberg quarry, Nieder-Beerbach, Odenwald, south-western Germany. It occurs as anhedral to subhedral flakes and grains up to 80 μm, associated with proustite and xanthoconite, on arsenolite, calcite and prehnite. Ferrofettelite is opaque with a metallic lustre and possesses a dark reddish-grey streak. It is brittle with an uneven fracture; the Vickers microhardness (VHN20) is 122 kg/mm2 (range 111–131). The calculated density is 5.74 g/cm3 (on the basis of the empirical formula). In plane-polarised reflected light, ferrofettelite is greyish white. Between crossed polars it is weakly anisotropic with red internal reflections. Electron-microprobe analyses give the chemical formula Ag16.04(Fe0.55Hg0.40Cu0.02)Σ0.97(As3.94Sb0.03)Σ3.97S15.02 on the basis of total atoms = 36.

Ferrofettelite is monoclinic, space group C2, with a = 26.011(2), b = 15.048(1), c = 15.513(1) Å, β = 90.40(1)° and V = 6071.9(7) Å3 for Z = 8. The six strongest Bragg peaks in the powder X-ray diffraction pattern (d, Å (I, %) (hkl) are: 3.18 (50) ($\bar{8}$01), 3.104 (100) (005), 3.004 (60) ($\bar{8}$02), 2.755 (40) ($\bar{4}$43), 2.501 (30) ($\bar{4}$44) and 1.880 (30) ($\overline {12}$40). The crystal structure can be described as the alternation of two kinds of layers along the c-axis: layer A with general composition [Ag6As2S7]2– and layer B with a general composition of [Ag10FeAs2S8]2+. In the structure, the Ag atoms adopt various coordinations extending from quasi linear to quasi tetrahedral, the AsS3 groups form pyramids as are typically observed in sulfosalts, and mixed (Fe,Hg) links two sulfur atoms in a linear coordination. Ferrofettelite is the first reported inorganic phase showing a linear coordination for Fe2+. The high-temperature behaviour of ferrofettelite was studied up to 410 K and compared to that of fettelite.

Stibiogoldfieldite, Cu12(Sb2Te2)S13, was approved as a new mineral species from the Mohawk mine, Goldfield mining district, Esmeralda County, Nevada, USA. It occurs as metallic anhedral grains, dark grey in colour. It is associated with quartz, pyrite and an Ag–Bi–(S,Se) phase (holotype material) and with quartz, pyrite, calaverite, bismuthinite, bohdanowiczite, and the Ag–Bi–(S,Se) phase (cotype material). In reflected light, stibiogoldfieldite is isotropic, grey in colour, with indistinct brownish shade. Reflectance data in air [R (%)] are: 31.1 at 470 nm, 30.9 at 546 nm, 30.8 at 589 nm and 31.0 at 650 nm. Electron microprobe analysis for holotype material gave (in wt.% – average of 60 spot analyses): Cu 45.03(60), Ag 0.26(7), Fe 0.02(3), Zn 0.13(15), Sn 0.02(4), Pb 0.05(6), Sb 8.02(62), As 2.80(65), Bi 2.77(87), Te 15.15(1.24), S 24.50(32), Se 0.52(11), total 99.27(69). On the basis of (As + Sb + Te + Bi) = 4 atoms per formula unit (apfu), the empirical formula of stibiogoldfieldite is (Cu12.05Ag0.04Zn0.03Fe0.01)Σ12.13(Sb1.12As0.63Bi0.23Te2.02)Σ4.00(S12.99Se0.11)Σ13.10. Chemical data on an additional sample from the same locality (cotype material) gave the following results (in wt.% – average of 181 spot analyses): Cu 43.84(63), Ag 0.21(7), Sb 5.92(78), As 2.63(45), Te 20.07(1.19), S 25.13(53), Se 0.97(35), total 99.47(66). On the basis of (As + Sb + Te + Bi) = 4 apfu, the empirical formula of cotype material is (Cu11.30Ag0.03)Σ11.33(Sb0.80As0.57Bi0.06Te2.57)Σ4.00(S12.83Se0.20)Σ13.03. Stibiogoldfieldite is cubic, I$\overline 4$3m, with unit-cell parameters a = 10.3466(17) Å, V = 1107.6(5) Å3 and Z = 2 (holotype). Unit-cell parameters for the cotype sample are a = 10.3035(2) Å and V = 1093.83(7) Å3. The crystal structure of holotype stibiogoldfieldite was refined by single-crystal X-ray diffraction data to a final R1 = 0.032 on the basis of 285 reflections with Fo > 4σ(Fo) and 20 refined parameters. Stibiogoldfieldite is isotypic with other members of the tetrahedrite group.

A nomenclature and classification scheme for wöhlerite-group minerals has been established. The general formula of minerals belonging to this group is given by X8(Si2O7)2W4, where X = Na+, Ca2+, Mn2+, Ti4+, Zr4+ and Nb5+; and W = F– and O2–. In addition, they may incorporate significant amounts of Mg2+, Fe2+, Y3+ and REE3+, where REE are the lanthanides. The main structural feature of these minerals is the four-columns-wide octahedral walls, which are interconnected through corner sharing and via the disilicate groups. The wöhlerite-group minerals crystallise in different unit-cell settings and symmetries, depending on the cationic ordering in the octahedral walls and the relative position of the disilicate groups. Different combinations of X and W constituents should be regarded as separate mineral species. In the case of coupled heterovalent substitutions at different crystallographic sites, it is advised to use the site-total charge approach to determine the correct end-member composition. Due to their structural and chemical features, wöhlerite-group minerals can easily form crystals with several micro domains, showing different crystal structures and chemical compositions. In addition, the crystallisation of polytypes is relatively common, although they should not be regarded as distinct mineral species. To date, ten minerals belonging to the wöhlerite group are considered as valid species: baghdadite, burpalite, cuspidine, hiortdahlite, janhaugite, låvenite, moxuanxueite, niocalite, normandite and wöhlerite. Låvenite and normandite are isostructural and are respectively the Zr and Ti end-members of a solid-solution series. Marianoite is discredited, as it is corresponds to wöhlerite. The ideal formula of hiortdahlite is revised as Na2Ca4(Ca0.5Zr0.5)Zr(Si2O7)2OF3, with one cationic site characterised by a valency-imposed double site-occupancy. These changes have been approved by the IMA–CNMNC (Proposal 20–D).

The provenance of raw materials and finished objects is one of the most intriguing problems in archaeology. It is significant for the discussion of inter-regional cultural communication. Many of the methods used to determine provenance employed by archaeologists are shared with geologists or geochemists, among which the use of lead isotopes is probably one of the best-known. However, geologists and archaeologists do not always ask the same questions. Because of many and various human choices, it is not always possible to apply geological methods directly to archaeological objects. Specifically, the potential existence of mixing and recycling of metals challenges all the provenance studies of metal objects. In this paper, using Bronze Age China as an example, we suggest that by using geochemical techniques such as lead isotopic analysis and trace-element analysis of bronzes, but by asking slightly different questions, one can throw new light on the way in which important resources were managed by consumers of different social status within early dynastic China.

Guite (IMA2017-080), Co3O4, is a new mineral species and an important economic mineral found in the Sicomines copper-cobalt mine, located ~11 km southwest of Kolwezi City, Democratic Republic of Congo. The mineral occurs as a granular agglomerate, 50 to 500 μm in size, and is associated closely with heterogenite in a quartz matrix. Guite is opaque, has a dark grey colour with metallic lustre and a black streak. In reflected light microscopy, it is white with no internal reflections. The reflectance values (in air, R in %) are: 27.0 (470 nm); 25.6 (546 nm); 25.2 (589 nm), and 24.6 (650 nm). The average of 20 electron-microprobe analyses is Co 71.53, Cu 0.58, Mn 0.67, Si 0.25, O 26.78, total 99.82 wt.%, corresponding to the empirical formula calculated on the basis of 4 O apfu: (Co2+0.92Cu2+0.02Si4+0.02)Σ0.96(Co3+1.98Mn3+0.03)Σ2.01O4.00, with Co2+ and Co3+ partitioned using charge balance. The ideal formula is Co2+Co3+2O4. Guite is cubic with space group Fd$\bar{3}$m. The unit cell parameters refined from the single crystal X-ray diffraction data are: a = 8.0898(1) Å, V = 529.436(11) Å3 and Z = 8. The calculated density of guite is 6.003 g/cm3. The eight strongest observed powder X-ray diffraction lines [d in Å (I/I0) (hkl)] are: 4.6714 (16.7) (111), 2.8620 (18.4) (220), 2.4399 (100) (311), 2.3348 (10.4) (222), 2.0230 (24.8) (400), 1.5556 (26.3) (511, 333), 1.4296 (37.7) (440) and 1.0524 (10.1) (731, 553). The crystal structure of guite was determined by single-crystal X-ray diffraction and refined to R = 0.0132 for 3748 (69 unique) reflections. Guite has a typical spinel-type structure with Co2+ in tetrahedral coordination with a Co2+–O bonding length of 1.941(1) Å, and Co3+ in octahedral coordination with a Co3+–O bonding length of 1.919(1) Å. The structure is composed of cross-linked framework of chains of Co3+–O6 octahedra sharing the equilateral triangle edges (2.550 Å) in three directions [0 1 1], [1 1 0], [1 0 1] with Co2+ filling the tetrahedral interstices among the chains. Guite is named in honour of Prof. Xiangping Gu (1964–).

The Altar Stone at Stonehenge in Wiltshire, UK, is enigmatic in that it differs markedly from the other bluestones. It is a grey–green, micaceous sandstone and has been considered to be derived from the Old Red Sandstone sequences of South Wales. Previous studies, however, have been based on presumed derived fragments (debitage) that have been identified visually as coming from the Altar Stone. Portable X-ray fluorescence (pXRF) analyses were conducted on these fragments (ex situ) as well as on the Altar Stone (in situ). Light elements (Z<37) in the Altar Stone analyses, performed after a night of heavy rain, were affected by surface and pore water that attenuate low energy X-rays, however the dry analyses of debitage fragments produced data for a full suite of elements. High Z elements, including Zr, Nb, Sr, Pb, Th and U, all occupy the same compositional space in the Altar Stone and debitage fragments, and are statistically indistinguishable, indicating the fragments are derived from the Altar Stone. Barium compares very closely between the debitage and Altar Stone, with differences being related to variable baryte distribution in the Altar Stone, limited accessibility of its surface for analysis, and probably to surface weathering.

A notable feature of the Altar Stone sandstone is the presence of baryte (up to 0.8 modal%), manifest as relatively high Ba in both the debitage and the Altar Stone. These high Ba contents are in marked contrast with those in a small set of Old Red Sandstone field samples, analysed alongside the Altar Stone and debitage fragments, raising the possibility that the Altar Stone may not have been sourced from the Old Red Sandstone sequences of Wales. This high Ba ‘fingerprint’, related to the presence of baryte, may provide a rapid test using pXRF in the search for the source of the Stonehenge Altar Stone.