Reaphookhillite, ideally MgZn2(PO4)2⋅4H2O, is a new phosphate mineral from Reaphook Hill, Flinders Ranges, South Australia, Australia. Reaphookhillite occurs as colourless, bladed to thin tabular crystals to 0.6 mm across. Cleavage is perfect parallel to {010}. The mineral occur as overgrowths on parahopeite crystals and is associated with scholzite, leucophosphite and chalcophanite. The calculated density is 3.09 g/cm3 from the empirical formula. Reaphookhillite is optically biaxial (+), α = 1.583(3), β = 1.596(3), γ = 1.611(3) and 2Vcalc = 88.7°. Electron microprobe analyses gave ZnO 41.57, MgO 7.96, MnO 0.40, P2O5 33.72, H2O(calc) 16.92, total 100.57 wt.%. The empirical formula, based on 12 O apfu, is Mg0.83Zn2.16Mn2+0.02(PO4)2.01⋅3.97H2O. Reaphookhillite is triclinic, P${\bar 1}$, with the unit-cell parameters of a = 5.7588(12), b = 7.5341(15) c = 5.2786(11) Å, α = 93.44(3), β = 91.27(3), γ = 91.30(3)°, V = 228.49(8) Å3 and Z = 1. The strongest eight lines in the powder X-ray diffraction pattern are [dobs in Å (I) (hkl)] 7.577 (100) (010); 4.461 (24) (01${\bar 1}$); 4.461 (24) (01${\bar 1}$); 3.771 (14) (020); 3.158 (13) (02${\bar 1}$); 2.982 (32) (021); 2.880 (27) (200); 2.775 (14) (1${\bar 2}$1, 12${\bar 1}$); and 2.668 (13) (1${\bar 2}{\bar 1}$, 210). Reaphookhillite is isostructural with parahopeite, with Mg replacing Zn in the 6-coordinated site in the structure. The structure contains ZnO4 and PO4 tetrahedra which share corners to form a sheet in the (001) plane. Sheets are linked in the c direction by corner sharing MgO2(H2O)4 octahedra.

Dendoraite-(NH4), (NH4)2NaAl(C2O4)(PO3OH)2(H2O)2, is a new mineral species 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 dendoraite-(NH4) are antipinite, fluorite, mimetite, mottramite, relianceite-(K), rowleyite, salammoniac, struvite, vanadinite, willemite, wulfenite and at least one other new mineral. Crystals of dendoraite-(NH4) are colourless blades up to ~0.1 mm in length. The streak is white and lustre is vitreous, Mohs hardness is 2½, tenacity is brittle and fracture is splintery. The calculated density is 2.122 g⋅cm–3. Dendoraite-(NH4) is optically biaxial (–) with α = 1.490(5), β = 1.540(5) and γ = 1.541(5) (white light); 2Vcalc = 15.7°; and orientation X = b. Electron microprobe analysis gave the empirical formula [(NH4)1.48K0.52]Σ2.00Na0.96(Al0.96Fe3+0.03)Σ0.99(C2O4)[PO2.97(OH)1.03]2(H2O)2, with the C, N and H contents constrained by the crystal structure. Dendoraite-(NH4) is monoclinic, P21/n, with a = 10.695(6), b = 6.285(4), c = 19.227(12) Å, β = 90.933(10)°, V = 1292(2) Å3, and Z = 4. The structural unit in the crystal structure of dendoraite-(NH4) (R1 = 0.0467 for 1322 Io > 2σI reflections) is a double-strand chain of corner-sharing AlO6 octahedra and PO3OH tetrahedra decorated by additional PO3OH tetrahedra and C2O4 groups. Topologically, this is the same chain found in the structure of thebaite-(NH4). The decorated chains connect to one another through links to NaO7(H2O) polyhedra to form a [Na(H2O)Al(C2O4)(PO3OH)2]2– sheet, which connect to one another through bonds to (NH4)/K and through hydrogen bonds.

Relianceite-(K), K4Mg(V4+O)2(C2O4)(PO3OH)4(H2O)10, is a new mineral species from the Rowley mine, Maricopa County, Arizona, USA. It occurs in an unusual bat-guano-related, post-mining assemblage of phases. Other secondary minerals associated with relianceite-(K) are antipinite, dendoraite-(NH4), fluorite, mimetite, mottramite, rowleyite, salammoniac, struvite, vanadinite, willemite, wulfenite and at least one other new mineral. Crystals of relianceite-(K) are sky blue prisms up to ~0.1 mm in length. The streak is very pale blue and lustre is vitreous, Mohs hardness is 2½, tenacity is brittle and fracture is splintery. The calculated density is 2.111 g⋅cm–3. Relianceite-(K) is optically biaxial (+) with α = 1.528(2), β = 1.529(2), γ = 1.562(2) (white light); 2Vmeas = 22(1)°; orientation Z = b; pleochroism: X = colourless, Y = pale blue, Z = pale blue; X < Y ≈ Z. Electron microprobe analysis gave the empirical formula [K2.21(NH4)1.79]Σ4.00Mg0.96(V4+0.95O)2(C2O4)[P1.03O3.03(OH)0.97]4(H2O)10, with the C, N and H contents constrained by the crystal structure. Raman spectroscopy confirmed the presence of NH4 and C2O4. Relianceite-(K) is monoclinic, Pc, with a = 12.404 (7) Å, b = 9.014 (6), c = 13.260 (8) Å, β = 100.803(10)°, V = 1456 (2) Å3 and Z = 2. The structural unit in the crystal structure of relianceite-(K) (R1 = 0.0540 for 3751 Io > 2σI reflections) is a (V4+O)2(C2O4)(PO3OH)4 chain in which VO6 octahedra are bridged by an oxalate group to form [V2C2O12] dimers, PO3OH tetrahedra form a double bridge between the VO6 octahedra of the dimers, and additional PO3OH tetrahedra decorate the chain. Topologically, this is the same chain found in the structure of davidbrownite-(NH4). The MgO(H2O)5 octahedron can be considered a distant decoration on the chain. The chains are linked to each other through an extensive system of K/NH4–O bonds and hydrogen bonds.

A new occurrence of kintoreite, ideally PbFe3(PO4)(PO3OH)(OH)6, is described from the Tripi mine, Alì, Peloritani Mountains, northeastern Sicily, Italy. Kintoreite occurs as yellow equant crystals, up to 0.05 mm in size, on quartz, associated with another alunite-supergroup mineral currently under study. The studied grains of kintoreite are chemically zoned, showing the occurrence of two distinct domains. Electron microprobe analyses gave (in wt.%): SO3 5.47(27), P2O5 17.55(14), Al2O3 7.81(35), Fe2O3 23.81(44), PbO 35.11(41), H2Ocalc 9.93, total 99.68 (darker domains) and SO3 6.03(5), P2O5 16.66(23), Al2O3 4.22(2), Fe2O3 27.31(6), PbO 33.78(22), H2Ocalc 10.25, total 98.25 (brighter domains). On the basis of 14 O atoms per formula unit (apfu) and (P+S) = 2 apfu, the darker and brighter domains have chemical formula Pb1.00(Fe3+1.89Al0.97)Σ2.86[P1.57S0.43O7.43(OH)0.57][(OH)5.58(H2O)0.42]Σ6.00 and Pb0.98(Fe3+2.21Al0.53)Σ2.74[P1.51S0.49O7.49(OH)0.51][(OH)5.18(H2O)0.82]Σ6.00, respectively. Single-crystal X-ray diffraction was performed on a grain extracted from the same sample. Unit-cell parameters are a = 7.2191(10), c = 16.834(3) Å, V = 759.8(3) Å3 and Z = 3; space group R$\bar{3}$m. The crystal structure was refined on the basis of 226 unique reflections with Fo > 4σ(Fo) and 31 least-square parameters to R1 = 0.0415. Kintoreite is isotypic with other alunite-supergroup minerals. Micro-Raman spectroscopy suggests the possible occurrence of H2O groups, supporting the possible protonation of (OH) groups as a charge-balance mechanism in this mineral. Kintoreite may play an environmental role in the Alì area, where previous authors detected high concentrations of potentially toxic elements in soils.

Calciolangbeinite, ideally K2Ca2(SO4)3, exists in two modifications, cubic and, first described in the present paper, orthorhombic. They are topologically-similar polymorphs which can be designated as calciolangbeinite-C and calciolangbeinite-O. Calciolangbeinite-O is the first natural orthorhombic langbeinite-like sulfate. It clearly differs from calciolangbeinite-C in the powder X-ray diffraction pattern, optical data and Raman spectrum. Calciolangbeinite-O is found in sublimates of the active Arsenatnaya fumarole at the Tolbachik volcano, Kamchatka, Far Eastern Region, Russia and in pyrometamorphic rocks of the Hatrurim Complex at Jabel Harmun, Judean Desert, Palestinian Autonomy and Har Parsa, Negev Desert, both in Israel. Calciolangbeinite-C is known only in fumarole sublimates at Tolbachik. Calciolangbeinite forms a continuous solid-solution system with langbeinite K2Mg2(SO4)3. The majority of the system is represented by cubic phases, and only members with compositions K2(Ca2.0–1.9Mg0.0–0.1)(SO4)3 have orthorhombic symmetry under room-temperature conditions. The crystal structure of calciolangbeinite-O was studied on a single crystal, chemically very close to K2Ca2(SO4)3, from Tolbachik (R1 = 2.75%). The unit-cell parameters are: a = 10.3330(2), b = 10.5027(2), c = 10.1763(2) Å, V = 1104.37(4) Å3 and Z = 4; space group is P212121. Calciolangbeinite-O is a low-temperature modification of K2Ca2(SO4)3 belonging to the K2Cd2(SO4)3 structure type whereas calciolangbeinite-C (space group P213), a high-temperature modification, has the langbeinite-type structure. The significant Mg admixture in calciolangbeinite-C from Tolbachik probably stabilises its cubic structure at room temperature. In both high-temperature fumaroles and pyrometamorphic rocks calciolangbeinite crystallises in the cubic modification, and during cooling its chemical variety close to the end-member K2Ca2(SO4)3 undergoes phase transition to calciolangbeinite-O, whereas the Mg-enriched varieties of the mineral remain calciolangbeinite-C.

Bridgesite-(Ce), (IMA2019-034), was discovered at Tynebottom Mine, Cumbria, UK. It occurs as thin (1–2 μm) translucent blue crystals with a lath-like to acicular habit, aggregated into thin crusts and is associated mainly with brochantite, malachite, serpierite, devilline, gypsum, aragonite, jarosite, pyrite, lanthanite-(Ce) and undifferentiated iron oxyhydroxides, it is often intergrown with these other minerals. The lustre, hardness, cleavage and parting could not be determined, nor could density be measured due to crystal size. It has a pale blue streak and is brittle with a splintery fracture. Bridgesite-(Ce) is biaxial (–), shows no pleochroism and has refractive indices (white light): α = 1.526(2), β = 1.564(2), γ = 1.572(2) and 2V(calc) = 48.3°. The empirical formula calculated on the basis of 44 negative charges is Ca0.86REEΣ1.99Al0.07Cu5.95(SO4)3.99(SiO4)0.05(PO4)0.02(OH)11.52⋅8H2O. The idealised formula is CaCe2Cu6(SO4)4(OH)12⋅8H2O, requiring (wt.%): 3.91 CaO, 22.89 Ce2O3, 33.28 CuO, 22.33 SO3 and 17.59 H2O. Bridgesite-(Ce) is monoclinic, space group C2/m, a = 24.801(5), b = 6.3520(13), c = 11.245(2) Å, β = 114.51(3)°, V = 1611.9(6) Å and Z = 2. The five most intense X-ray diffraction peaks in the measured pattern are [d in Å (I, %) (hkl)]: 11.3 (100) (200), 6.391 (15) (201), 2.770 (8) (420), 3.194 (6) (402) and 4.858 (5) (310). The crystal structure was solved using single crystal data and refined to an R1 index of 5.86%. Bridgesite-(Ce) contains three distinct Cu sites containing Cu2+, two are coordinated octahedrally and one is square pyramidal. The octahedra form chains through edge sharing parallel to the b-axis which are linked by the square pyramid to form sheets oriented parallel to {100}. Sulfate tetrahedra decorate the sheets which are held together by interstitial REE3+, Ca2+ and hydrogen bonding. The structure is unique. Despite apparent similarity in chemical formula, bridgesite-(Ce) is not closely related to any other natural Cu-sulfate mineral. An FTIR absorption spectra is presented for reference purposes.

Sluzhenikinite, Pd15(Sb7–xSnx) with 3 ≤ x ≤ 4, is a new mineral discovered in the pegmatoidal galena–chalcopyrite massive ore from the Oktyabrsk mine, Oktyabrsk deposit of the Noril`sk deposits, Russia. Sluzhenikinite forms euhedral elongate lamellar crystals (100–150 μm long and 10–50 μm wide) associated with Au–Ag alloy, insizwaite and myrmekitic intergrowths of Pt–Pd minerals (stibiopalladinite, maslovite and sobolevskite), in close association of sperrylite and base-metal sulfides (galena, chalcopyrite, cubanite and pentlandite). In plane-polarised light, sluzhenikinite is pale brown with weak bireflectance, imperceptible pleochroism, and weak anisotropy with straw yellow to deep blue rotation tints; it exhibits no internal reflections. Reflectance values for sluzhenikinite in air (R1,R2 in %) are: 46.2, 46.5 at 470nm; 52.1, 52.2 at 546nm; 54.7, 55.1 at 589nm; and 57.8, 59.0 at 650nm. Thirteen electron-microprobe analyses of sluzhenikinite gave an average composition: Pd 65.06, Sn 15.60 and Sb 19.58, total 100.24 wt.%, corresponding to the formula Pd14.88(Sb3.92Sn3.20)Σ7.12 based on 22 atoms; the average of twenty-one energy dispersive spectroscopy analyses on co-type material gave: Pd 63.36, Pt 1.15, Sn 16.28 and Sb 19.21, total 100.00 wt.%, corresponding to the formula (Pd14.62Pt0.14)Σ14.76(Sb3.87Sn3.37)Σ7.24. The density, calculated on the basis of the empirical formula, is 11.22 g/cm3. The mineral is monoclinic, space group P21/m, with a = 7.5558(1), b = 29.2967(3), c = 7.5713(1) Å, β = 119.931(2)°, V = 1452.44(4) Å3 and Z = 4. The crystal structure was determined using data from single-crystal X-ray diffraction and demonstrates conclusively that the correct stoichiometry is Pd15(Sb,Sn)7, rather than Pd2(Sb,Sn); R1 = 0.035, wR2 = 0.073, GoF = 1.118 for 209 refined parameters and 4738 unique reflections. The mineral is named after Sergey Fedorovich Sluzhenikin, an expert on platinum-group minerals, particularly from the area of the type locality.

Two contrasting reaction coronae were developed around rare earth element (REE) accessory phosphates in Variscan metagranitic rocks, which have been overprinted by Alpine blastomylonitisation from the Fabova Hol'a Massif, in the Veporic Unit, Western Carpathians, Central Slovakia. The Th–U–Pb total EPMA age determination of primary magmatic monazite-(Ce) from the metagranite indicates a Carboniferous (Mississippian, Tournaisian) age of 355 ± 1.9 Ma. Monazite-(Ce) breakdown resulted in impressive, though common, fluorapatite ± Th-silicate + allanite-(Ce) + clinozoisite coronae. The alteration of xenotime-(Y) produced a novel type of secondary coronal micro-texture consisting of a massive fluorapatite mantle zone and tiny satellite crystals of hellandite-(Y) [(Ca,REE)4Y2Al□2(B4Si4O22)(OH)2] and hingganite-(Y) [Y2□Be2Si2O8(OH)2] of ~1–5 μm, and rarely ≤10 μm in size. The localised occurrence of Y–B–Be silicates, which are associated closely with other secondary minerals, suggests the involvement of B and Be during the metasomatic alteration transformation of xenotime-(Y). General reactions for monazite-(Ce) and xenotime-(Y) decomposition, including the fluids involved, can be written as follows: Mnz + (Ca, Fe, Si, Al and F)-rich fluid → FAp + Ht + Aln + Czo; Xtm + (Ca, Fe, Si, Al, F, B and Be)-rich fluid → FAp + Hld + Hin + Czo.

The granitic rocks underwent Early Cretaceous burial metamorphism under greenschist- to lower amphibolite-facies P–T conditions. Subsequently, Alpine post-collisional uplift and exhumation of the Veporic Unit, starting from the Late Cretaceous epoch, was accompanied by a retrograde tectono-metamorphic overprint; the activity of external fluids, caused the formation of secondary coronae minerals around monazite-(Ce) and xenotime-(Y). A portion of B (± Be) should have been liberated from the metagranite feldspars, micas, or xenotime-(Y) enriched in (Nb,Ta)BO4 (schiavinatoite or béhierite) components. However, the principal source of B and Be in fluids necessary for the production of hellandite and hingganite, was probably of external origin from adjacent magmatic, metamorphic, or sedimentary rocks (Permian granites, rhyolites and sedimentary rocks, and Palaeozoic metapelites).

The Wombat Hole Prospect is a small copper–bismuth–(tellurium) exoskarn cropping out in the Morass Creek gorge, near Benambra, in eastern Victoria, Australia. Its main primary sulfide constituent is bornite in a grossular‒vesuvianite matrix. The skarn formed in a megaclast of Lower Silurian limestone from metal-bearing fluids accompanying the high-level emplacement of the Late Silurian–Lower Devonian Silver Flat Porphyry. Though the primary bornite mineralisation has been nearly obliterated by weathering, there are small relict patches containing exsolved grains of wittichenite (Cu3BiS3) and chalcopyrite, as well as inclusions of bismuth tellurides in the tetradymite group, namely sulphotsumoite (Bi3Te2S) and hedleyite (Bi7Te3). Joséite-A (Bi4TeS2), a mineral with a formula Bi3(Te,S)4, several unnamed Cu–Bi‒Te phases and minute grains of native bismuth have also been detected. Pervasive veining by chrysocolla throughout the garnet‒vesuvianite host contains a range of unusual secondary bismuth minerals that have crystallised at various times. These include mrázekite, namibite, pucherite, schumacherite and eulytine. Other secondary minerals present include wulfenite, bismutite, azurite, malachite and a poorly-crystalline bismuth oxide containing several weight percent tellurium. Rare grains of gold (electrum) containing up to 23 wt.% Ag are also present. The assemblage of grossular–vesuvianite with minor diopside is indicative of formation in a low-${\rm X}_{{\rm C}{\rm O}_ 2}$ environment under fluid-buffered conditions. A temperature range between ~650°C and as low as ~150°C can be estimated from the exsolution of wittichenite and chalcopyrite from the bornite. The tetradymite-group inclusions formed first under low values of $f_{{\rm S}_ 2}$ /$f_{{\rm T}{\rm e}_ 2}$, with bornite crystallising as values increased. The primary Cu‒Bi‒Te mineralogy and the unusual secondary mineral assemblage makes the Wombat Hole skarn unique in southeastern Australia. The deposit provides scope for studying the mobility of elements such as Bi and Te over short distances during weathering of hypogene ore minerals.

The Devonian Hera metaturbidite-hosted polymetallic Au–Zn–Pb–Ag deposit of central NSW, Australia, contained a total undepleted resource of 3.6 Mt @ 3.3 g/t Au, 25 g/t Ag, 2.6% Pb and 3.8% Zn. The deposit comprises a number of distinctive lodes with each containing a distinctive ore and alteration/gangue mineralogy, though generally the sulfide ore comprises various mixtures of sphalerite, galena, chalcopyrite, pyrrhotite and relatively common visible gold–electrum. The North Pod and Far West lodes are distinctly Sb rich and contain a more diverse ore mineralogy with arsenopyrite, native silver, native antimony, gudmundite, tetrahedrite-(Fe), argentotetrahedrite-(Fe), acanthite, dyscrasite, nisbite and breithauptite. From analysis of 52,760 assays from across the deposit it was found that there was a very poor correlation between gold and each of Fe, Zn, S, Pb, Cu, As and Ag, whereas Ag correlated reasonably well with both Pb and Zn. Results from EPMA shows that gold varies widely in composition from host-rock associated gold (96 wt.% Au) through more intermediate compositions (88–73 wt.% Au) to electrum (46–27 wt.% Au), commonly associated with Sb-phases and containing significant Sb within the gold itself (1.05–2.58 wt.% Sb). From the Far West lense, aurostibite occurs as distinctive rims around gold. Although aurostibite associated with gold contains no silver, the gold itself contains constant moderate amounts (10.87–12.27 wt.% Ag). We suggest that the aurostibite and other Sb phases formed from a late-stage Sb-rich hydrothermal during low-temperature retrograde skarn alteration. There is abundant evidence for both chemical and physical remobilisation at Hera and this remobilisation is largely responsible for the spectrum of gold compositions observed. The source for these fluids may be an underlying magmatic body, evidence for which occurs as granite pegmatite dykes in various locations throughout the deposit. Furthermore, gold with a moderate to high Sb content may be indicative of a low temperature of formation.

The Girilambone copper deposit of New South Wales, Australia, serves as an end-member model for development of a classic oxidation-zone profile in an environment virtually free of both the effects of active tectonics and significant fluctuation in the local water table. The oxidation zone of other copper deposits may be interpreted for history of recently active tectonics, palaeoclimate, and water-table stability by comparison to the Girilambone deposit. Unlike the oxidation profiles of porphyry copper deposits of western North America, which have been overprinted by many water-table fluctuations produced by active tectonics, the Girilambone deposit appears to have little modification to the original oxidation profile. Oxidation of primary sulfides at Girilambone was an exothermic process facilitated by chemolithotrophic bacteria, recorded by malachite oxygen isotope thermometry estimates of up to 52°C, and very light malachite carbon isotope values. The bacteria generated CO2 which migrated upwards to react with copper rich meteoric fluids of the vadose zone to precipitate malachite. Unlike porphyry copper deposits of western North America which experienced recent tectonic activity, the secondary minerals (clays, iron oxides and copper carbonates) at Girilambone were not repeatedly fractured and offset during oxidation to re-establish permeability. This reduced permeability of the oxidation zone and slowed the release of CO2 from the system, producing significantly elevated partial pressure of CO2, sufficient for azurite formation to dominate. Azurite oxygen and carbon isotope values indicate formation at lower temperatures up to 32°C, and with less bacterial activity than for malachite. The sulfide-digesting bacteria at Girilambone were relatively free of seasonal swings in population, as the deposit does not have the interbanded azurite and malachite typical of episodic bacterial populations triggered by seasonal precipitation. Thus the absence of significant Cu-carbonate banding at Girilambone serves as a palaeoclimate indicator. Deeper in the Girilambone oxidation zone, native copper and cuprite dominate, whereas chalcocite formed an enrichment blanket just above and at the modern water table. Oxygen and carbon isotope values for pseudomorphs of malachite after azurite indicate that these were generated as a retrograde reaction when CO2 production from bacterial digestion of sulfides waned and temperatures in the oxidation zone were near ambient. In the post mining environment, chloride-rich groundwater seeps actively precipitate atacamite, while exposed remnants of sulfide masses form an outer rind of porous malachite. Exceptions to this oxidation zone sequence occur due to localised fluid channelisation and perched water-table lenses that generated mineralogical overprints.

Fractionation factors for the isotopes of O, H, S, or Cu (as appropriate) were determined for the minerals brochantite [Cu4(SO4)(OH)6], libethenite [Cu2(PO4)(OH)] and olivenite [Cu2(AsO4)(OH)] and corresponding aqueous solutions at temperatures between 30 and 70°C. All samples used for this determination were synthetic and the degree of fractionation was expressed as 1000 ln α = (A × 106/T2) + B, where A and B are empirical parameters. A few natural libethenite samples from its type locality Ľubietová-Podlipa were also analysed and compared to the prediction based on the isotopic composition of meteoric water and our fractionation factors. The hydrogen fractionation factors agreed with the prediction well, whereas those for oxygen did not. A possible explanation is the disequilibrium of aqueous phosphate (and also arsenate) species and the solution in our experiments or the interaction of meteoric fluids with the isotopically heavy (in terms of oxygen) country rocks. Because the effects of isotopic disequilibrium in our experiments cannot be ruled out, the oxygen fractionation factors should be used with caution. The determined fractionation factors can be used as an isotope geothermometer, given that it can be proven that the phases of interest precipitated from the same fluid in equilibrium. Libethenite is predicted to have slightly lower δ65Cu values than its parental solution, but brochantite slightly higher δ65Cu values than its parental solution. Simple forward models, simulating neutralisation or reduction of mine drainage, show that precipitation of these minerals and removal of the co-existing fluid, could cause isotopic variations (in δ65Cu) on the order of 1‰ or more.

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.

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.

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.

Two hundred years (1750–1950) of earthen architecture represents an important period of construction in the central region of Portugal. Earthen architecture is usually built close to the coast or to rivers and placed in sandy ground. The impact of rising damp is a general problem and efflorescences are a common cause of damage decay. This problem was studied in a building with two types of earthen construction, adobe masonry walls and formed masonry walls. The aim of this research was to characterise the conditions for the appearance and phase transitions of thénardite and mirabilite, and determine how to prevent progression of salt effects in the two types of wall to support future conservation measures. Laboratory capillarity and porosimetry tests with dolomitic air lime mortar and hygrothermal monitoring were pursued along with in situ tests. Visual assessment showed that the progression of salts depends on the composition of the earthen materials. To understand these differences, all crystalline solid phases were analysed by powder X-ray diffraction, and building interior hygrothermal conditions were monitored. An investigation into the influence of surface lime water painting and sacrificial mortar application on the crystallisation of sodium sulfates concluded that these also depend on the wall's composition. Data allowed us to conclude that inside the building the temperature and humidity [relative humidity (RH = 100 pw/p°w > 70)] conditions led to the adobe breakdown by the fast conversion from thénardite to mirabilite. Therefore, contact with wet atmospheres should be avoided and interior hygrothermal conditions should be controlled. Laboratory and in situ tests showed that the environmental conditions of the spaces had effects on the results. The results contribute to understanding of the salt progression and pattern of decay, as well as supporting future recommendations for building conservation, based on the identification of environmental conditions proper to their occurrence.