Reznitskyite, ideally CaMg(VO4)F, is a new mineral species of the tilasite group from the Arsenatnaya fumarole, Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It occurs as zones (usually up to 0.05 mm thick) in crystals of V- and P-containing tilasite or as homogeneous grains up to 0.1 mm across. It was found in polymineralic sublimate encrustations in association with minerals of the svabite–fluorapatite–pliniusite system and the schäferite–berzeliite, tilasite–isokite, wagnerite–arsenowagnerite and udinaite–arsenudinaite series. The mineral assemblage also includes calciojohillerite, diopside, forsterite, titanite, rhabdoborite-(V), rhabdoborite-(W), rhabdoborite-(Mo), ludwigite, powellite, scheelite, hematite, baryte and magnesioferrite. Reznitskyite is transparent or semi-transparent, colourless, with vitreous lustre. Dcalc. = 3.453 g cm–3. Under the microscope, in reflected light reznitskyite is grey, non-pleochroic, with very weak bireflectance (ΔR589 nm = 0.5%) and distinct anisotropy. Reznitskyite is the first vanadate with a titanite-type structure. It is monoclinic, space group C2/c, a = 6.6912(7), b = 8.9395(7), c = 7.0587(8) Å, β = 113.078(13)°, V = 388.43(8) Å3 and Z = 4. The strongest reflections of the powder X-ray diffraction pattern are [d in Å(I)(hkl)]: 3.082(100)(200), 3.250(66)($\bar{1}$12, 002), 2.631(44)(022), 2.854(34)($\bar{2}$02), 2.683(33)(130), 3.686(26)(021), 2.531(25)(220), 1.749(25)($\bar{3}$32, $\bar{2}$04) and 2.344(24)(131). Electron microprobe analysis gave (wt.%) MgO 20.44, CaO 26.83, P2O5 6.24, V2O5 21.09, As2O5 18.97, SO3 0.47, F 9.42, –O=F –3.97, with a total of 99.49. The empirical formula of reznitskyite, calculated on the basis of O+F = 5 atoms per formula unit, is: Ca0.97Mg1.03(V0.47As0.33P0.18S0.01)Σ0.99O3.99F1.01. Reznitskyite is a vanadate analogue of tilasite CaMg(AsO4)F and isokite CaMg(PO4)F. The mineral is named in honour of the outstanding Russian mineralogist Leonid Zinovievich Reznitsky (born 1938) who has made significant contribution to the mineralogy of vanadium.

Magnesiobermanite, MgMn3+2(PO4)2(OH)2⋅4H2O, is a new secondary phosphate mineral and the Mg analogue of bermanite found in a granitic pegmatite at the White Rock No.2 quarry situated in the Bimbowrie Conservation Park, South Australia, Australia. Magnesiobermanite occurs as aggregates of twinned, bladed to tabular crystals, up to 1.2 mm across. Individual crystals are up to 0.3 mm in length. The crystals are orange–red to brownish red, with a vitreous lustre and a salmon-pink streak. The mineral is brittle with a conchoidal fracture and a good cleavage on {100}. The mineral is biaxial (–), with α = 1.690(2), β = 1.719(2) and γ = 1.734(2) (white light). The calculated 2V is 70.4°. Electron microprobe analyses provided: MgO 9.59, Mn2O3 27.41, Fe2O3 8.84, Al2O3 0.18, P2O5 33.27, H2O 20.94, total 100.23 wt.%. The empirical formula (based on 14 O atoms) is: Mg1.02(Mn3+1.49Fe3+0.47Al0.02)1.98(PO4)2.01(OH)1.95⋅4.01H2O. Magnesiobermanite is monoclinic, space group P21, with the unit-cell parameters: a = 5.4215(11), b = 19.072(4), c = 5.3889(11) Å, β = 110.21(3)°, V = 522.89(18) Å3 and Z = 2. The crystal structure was refined to an R1 index of 2.43% based on for 3222 observed reflections with Fo > 4σ(Fo). Magnesiobermanite is isostructural with bermanite, Mn2+Mn3+2(PO4)2(OH)2⋅4H2O, from which it derives its name. The structure is based upon a sheet of the form [(M(OH)2(PO4)2] in the (010) plane. Sheets are linked in the b direction by [M3(H2O)4O2] octahedra and by hydrogen bonds.

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 new mineral marchettiite (IMA2017-066) is the natural equivalent of ammonium hydrogen urate. It has a simple molecular formula C5H7N5O3 and can be alternatively written as (NH4)C5H3N4O3. Marchettiite was found in a cleft at Mount Cervandone, Devero Valley, Piedmont, Italy, where it occurs as aggregates of opaque pale pink to white, platy prismatic crystals. This mineral has a white streak, dull and opaque lustre, it is not fluorescent and has a hardness of 2–2.5 (Mohs’ scale). The tenacity is brittle and crystals have a good cleavage parallel to {001}. The calculated density is 1.69 g/cm3. Marchettiite is biaxial (–) with 2V of 47.24°; the optical properties of marchettiite were determined by periodic-DFT methods providing the following values: α = 1.372, β = 1.681 and γ = 1.768. No twinning was observed. Electron microprobe analyses gave the following chemical formula: C4.99H6.97N4.91O3.00. Although the small crystal size did not allow refinement of structural data by single-crystal diffraction, we were able to refine the structure by powder micro X-ray diffraction. Marchettiite has space group P$\bar{1}$ and the following unit-cell parameters: a = 3.6533(2) Å, b = 10.2046(7) Å, c = 10.5837(7) Å, α = 113.809(5)°, β = 91.313(8)°, γ = 92.44(1)° and V = 360.312 Å3. The strongest lines in the powder diffraction pattern [d in Å (I)(hkl)] are: 9.784(50)(001); 8.663(80)(01$\bar{1}$); 5.659(100)(011); 3.443(100)(10$\bar{1}$); 3.241(70)(003) and 3.158(100)(1$\bar{1}\bar{1})$. Marchettiite is named after Gianfranco Marchetti, the mineral collector who found this mineral.

A rare earth element (REE)-, Cr- and Mg-bearing variety of the vanadium epidote-group mineral mukhinite occurs in a calcite–dolomite carbonatite dyke cutting metamorphosed volcano-sedimentary rocks exposed in the walls of the quarry of the Svetlinsky gold deposit, South Urals. This mineral was found in a paragene assemblage including native sulphur, phlogopite and fluorophlogopite, together with accessory pyrite, other sulfides and sulfosalts, gold, Cr- and V-bearing muscovite, margarite, Cr- and V-bearing dravite, fluoro-tremolite, actinolite, fluoro-pargasite, anhydrite, apatite, uranium hydroxides, V-rich titanite, V- and Nb-rich rutile, spinel and corundum. The contents of ΣREE2O3 and V2O3 in mukhinite vary in the ranges of 4.01–9.69 and 5.34–7.46 wt.%, respectively. A Raman spectrum of REE-rich mukhinite is provided. The main schemes of isomorphic substitutions in mukhinite are ΣREE + Mg ↔ Ca + Al and V+Cr ↔ Al. The crystal structure of REE-rich mukhinite has been studied by single-crystal X-ray diffraction analysis. The mineral is monoclinic, with the space group P21/m, and unit-cell parameters are: a = 8.8972(11) Å, b = 5.6221(6) Å, c = 10.1519(12) Å, β = 115.169° and V = 459.60(11) Å3. The crystal structure of REE-rich mukhinite is similar to that of its synthetic analogue; the refined crystal-chemical formula of the sample studied is (Z = 2): {A1CaA2(Ca0.8REE0.2)}{M1(Al0.95Cr0.05)M2AlM3[(V,Cr)3+0.40Al0.35Mg0.25]}(Si2O7)(SiO4)O(OH).

Kingsgateite, ZrMo6+2O7(OH)2⋅2H2O, is a new supergene mineral from the Old 25 Pipe, Kingsgate, Gough Co., New South Wales, Australia. The mineral occurs in cavities in a quartz, muscovite matrix associated with molybdenite, gelosaite and mambertiite. It forms yellowish green to bluish grey, square tabular crystals to 0.12 mm across. Kingsgateite has a white streak and a vitreous lustre. Cleavage was not observed and the fracture is uneven. The calculated density is 3.74 g/cm–3 based on the empirical formula. Kingsgateite is optically biaxial (+), the calculated indices of refraction are α = 1.88, β = 1.89, γ = 1.96 and 2Vcalc = 42.6°. The pleochroism is X = light orange, Y = light yellow and Z = red brown; Y < X < Z. The mineral is tetragonal, space group I41cd, a = 11.4626(16), c = 12.584(3) Å, V = 1653.4(6) Å3 and Z = 8. Electron microprobe analysis yielded ZrO2 23.09, UO2 1.14, ThO2 0.76, FeO 0.62, MoO3 59.27, P2O5 0.29, SO3 1.25, Cl 0.16, H2O 11.62, O=Cl –0.04, total 98.16 wt.%. The empirical formula on the basis of 11 anions per formula unit is Zr0.88U6+0.02Th0.01Fe2+0.04Mo6+1.94S0.07P0.02O6.90Cl0.02OH2.08⋅2.00H2O. The crystal structure of kingsgateite, refined using synchrotron single-crystal data [R1 = 4.53% for 1159 reflections with Fo > 4σ(Fo)], is a framework of edge- and corner-sharing ZrO5(OH)2 pentagonal bipyramids and MoO4(OH)(H2O) octahedra. Kingsgateite is isostructural with the synthetic compound ZrMo6+2O7(OH)2⋅2H2O.

The synthetic analogue of mineral stillwaterite, Pd8As3, was synthesised and its crystal structure was solved to R1 = 0.0341 based on single crystal X-ray diffraction data. Pd8As3 is trigonal and the space group is P$\bar{3}$. The unit-cell parameters are a = 7.4261(4), c = 10.3097(9) Å and V = 492.38(7) Å3 with Z = 3. The structure builds up by layers of Pd and As atoms. Pd-nets and As-nets are parallel to (110) and stack along the c axis direction. The stacking sequence is ABCDEEDCBA. The relation between structures of minerals with the common formula Pd8T3 (T = As or/and Sb) are discussed. They are formed by nets of pnictogen and palladium atoms. The common feature of the structures is 36 topology of pnictogen nets. The differences are stacking sequences and topology of the palladium nets.

Wodegongjieite occurs in the Cr-11 chromitite orebody of the Luobusa ophiolite in the Kangjinla district, Tibet, China. It is found in two inclusions in corundum: (1) as a partial overgrowth (holotype) up to 1.5 μm thick around a spheroid 20 μm across of wenjiite (Ti10(Si,P,□)7), kangjinlaite (Ti11(Si,P)10), zhiqinite (TiSi2) and badengzhuite (TiP), and (2) as pools up to 0.25 μm wide filling interstices between wenjiite, jingsuiite (TiB2), osbornite–khamrabaevite (Ti[N,C]) and corundum. Energy dispersive analyses gave Al2O3 34.09, SiO2 49.11, K2O 2.56, CaO 11.71, SrO 2.53, total 100.0 wt.%, corresponding to K0.58Sr0.26Ca2.25Al7.20Si8.80O31.20, ideally KCa3(Al7Si9)O32, for Si + Al = 16 cations.

Single-crystal studies were carried out with three-dimensional electron diffraction providing data for an ab initio structure solution in the hexagonal space group P6/mcc (#192) with a = 10.2(2) Å, c = 14.9(3) Å, V = 1340(50) Å3 and Z = 2. Density (calc.) = 2.694 g⋅cm–3. The refinement, which assumes complete Si–Al disorder, gives average T1–O and T2–O bond lengths both as 1.65 Å. It was not practical to use unconstrained refinement for the occupancies of the large cation sites 6f and 2a. The ab initio model shows clearly that the two cation sites have different sizes and coordination. Consequently, we imposed the condition (1) that all the K occupies the 2a site as the average K–O bond length of 3.07 Å is close to the average K–O bond lengths reported in kokchetavite and (2) that all the Ca occupies the 6f site as the average Ca–O bond length of 2.60 Å (2.36 Å and 2.84 Å for Ca–O1 and Ca–O3, respectively) is reasonable for Ca–O. Assuming that all K and all Ca are located at the 2a site and 6f site, respectively, Sr occupancies of these sites could be refined. Thermal parameters are positive and in a reasonable range. The structure is a sheet silicate isostructural with the K-feldspar polymorph kokchetavite, with two crystallographically distinct sites for K, but not with the topologically identical anorthite polymorph dmisteinbergite (CaAl2Si2O8) with only a single site for Ca. Substitution of K by Ca at the 6f site is associated with marked rotation of the Si,Al tetrahedra and a collapse of the structure to accommodate the smaller Ca ion.

The spheroid of intermetallic phases is believed to have formed from the interaction of mantle-derived CH4 + H2 fluids with basaltic magmas at depths of ~30–100 km, resulting in precipitation of corundum that entrapped intermetallic melts. Associated immiscible silicate melt of granodioritic composition crystallised metastably to wodegongjieite instead of a mixture of anorthite and K-feldspar.

The crystal structure of hiärneite has been refined from single-crystal X-ray diffraction data (λ = 0.71073 Å) on type material from Långban, Värmland, Sweden. The refinement converged to R1 = 0.046 based on 1073 reflections with F2 > 4σ(F2). The tetragonal unit cell, space group I41/acd, has the parameters a = 15.2344(6) Å and c = 10.0891(6) Å with Z = 8. The mineral is isostructural with calzirtite, ideally Ca2Zr5Ti2O16, with a structural topology derived from fluorite. In hiärneite, Mn3+ is ordered at a 4- to 8-fold coordinated site (with a distorted polyhedral coordination figure), without the atom splitting encountered at the corresponding Zr-dominated site of calzirtite. The end-member formula for hiärneite is established as Ca2Zr4Mn3+SbTiO16. The calzirtite group, with calzirtite, hiärneite and tazheranite (cubic ZrO2-x), has been approved by the IMA–CNMNC.

We report the crystal structure of allanite-(Ce), with composition (Ca1.0REE0.9□0.1)Σ2.0(Al1.46Fe3+0.52Fe2+0.76Mg0.12Ti0.15)Σ3.01Si3O12(OH) from the Xinfeng rare earth element (REE)-bearing granite in Guangdong Province, China. It has the unit cell a = 8.9550(4) Å, b = 5.77875(16) Å, c = 10.2053(4) Å, β = 114.929(5)° and Z = 2 in space group P21/m and is characterised by site splitting at M3 into M3a and M3b, at a distance of 0.38(3) Å, which are occupied partially by Fe0.764Mg0.12 and Ti0.15, respectively. The structure was determined by single-crystal X-ray diffraction and refined with anisotropic full-matrix least-squares refinement on F2 to R1 = 2.82%, wR2 = 7.77% for 1856 independent reflections (8772 collected reflections). However, M3 splitting is not present in either ferriallanite-(Ce) or epidote, in which M3 is almost fully occupied either by Fe2+ or by Fe3+. Comparisons of bond lengths and volumes in cation polyhedra among allanite-(Ce), ferriallanite-(Ce) and epidote tend to indicate that the essential factor that facilitates site splitting of M3 in allanite-(Ce) is heterovalent substitution and occupation of a crystallographic site between Fe2+(Mg2+/Mn2+)–Al3+(Ti4+), a common phenomenon in minerals, such as the plagioclase series. Fine structure analysis of the M3 split model revealed that deformation of A2 is related closely to distorted M3, which is consistent with Fe2+ incorporation following REE substitution.

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.

Tennantite-(Cd), Cu10Cd2As4S13, was approved as a new mineral species from the Berenguela mining district, Pacajes Province, La Paz, Bolivia. It occurs as black metallic anhedral grains, up to 1 mm across, associated with baryte, montmorillonite and secondary Cd-sulfates (aldridgeite, niedermayrite and voudourisite). In reflected light, tennantite-(Cd) is isotropic and grey with brownish tints. Reflectance data for the four COM wavelengths in air are [λ (nm): R (%)]: 470: 30.0; 546: 30.1; 589: 28.2; and 650: 25.8. Electron microprobe analysis gave (in wt.% – average of 11 spot analyses): Cu 40.56(32), Ag 0.05(5), Fe 0.04(1), Zn 1.91(63), Cd 11.32(1.09), Hg 0.04(7), As 19.04(43), S 26.78(30), total 99.74(53). On the basis of ΣMe = 16 atoms per formula unit (apfu), the empirical formula of tennantite-(Cd) is Cu9.98Ag0.01Cd1.57Zn0.46Fe0.01As3.97S13.05. Tennantite-(Cd) is cubic, I$\bar{4}$3m, with unit-cell parameters a = 10.3088(2) Å, V = 1095.53(6) Å3 and Z = 2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1 = 0.0152 on the basis of 359 unique reflections with Fo > 4σ(Fo) and 22 refined parameters. Tennantite-(Cd) is isotypic with other tetrahedrite-group minerals. Its crystal-chemistry is discussed and previous findings of Cd-rich tetrahedrite-group minerals are briefly reviewed.

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.

Argentotetrahedrite-(Zn), Ag6(Cu4Zn2)Sb4S13, has been approved as a new mineral species by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA-CNMNC) using samples from Kremnica, Slovak Republic (hereafter KR), and Lengenbach, Switzerland (LE). Additionally, it was also identified at the small deposit of Zvěstov (Stříbrnice), Czech Republic (ZV). At the Slovak locality, it occurs as anhedral grains up to 0.1 mm in size, steel-grey in colour, with a metallic lustre, in association with ‘argentotennantite-(Fe)’ and tiny chalcopyrite grains in quartz gangue. At Lengenbach, it was found as domains of tristetrahedral crystal of tetrahedrite-(Zn), up to 1 mm in size, associated with dolomite. At Zvěstov, it occurs as irregular aggregates, up to 0.2 mm in size, partly rimmed by kenoargentotetrahedrite-(Fe). Argentotetrahedrite-(Zn) is isotropic, grey in colour, with blue-greenish tints. Reflectance data for COM wavelengths in air (KR sample) are [λ (nm), R (%)]: 470, 30.1; 546, 29.8; 589, 29.8; and 650, 28.3. Chemical formulae of the samples studied, recalculated on the basis of ΣMe = 16 apfu (atoms per formula unit), are: (Ag3.27Cu2.69)Σ5.96[Cu4.00(Zn1.69Fe0.23Cu0.05Cd0.02Hg0.01)Σ2.00](Sb3.86As0.17)Σ4.03S12.73 (KR), (Ag3.17Cu2.79)Σ5.96[Cu4.00(Zn1.55Cd0.23Fe0.16Cu0.05Hg0.01)Σ2.00](Sb3.71As0.32)Σ4.03S12.77 (LE) and (Ag3.27Cu2.67)Σ5.94[Cu4.00(Zn1.39Fe0.50Cu0.07Cd0.03Hg0.01)Σ2.00](Sb4.03As0.04)Σ4.07S13.08 (ZV). Argentotetrahedrite-(Zn) is cubic, I$\overline 4$3m, with a = 10.5505(10) Å, V = 1174.4(3) Å3 and Z = 2 (KR); a = 10.5155(13) Å and V = 1162.8(4) Å3 (LE); and a = 10.5663(12) Å and V = 1179.7 Å3 (ZV). The crystal structure of argentotetrahedrite-(Zn) has been refined by single-crystal X-ray diffraction data to a final R1 = 0.035 on the basis of 327 unique reflections with Fo > 4σ(Fo) and 22 refined parameters (sample KR). Argentotetrahedrite-(Zn) is isotypic with other members of the tetrahedrite group. The structural relationship between argentotetrahedrite-(Zn) and other members of the freibergite series are discussed and previous findings of this species are briefly reviewed.

The new mineral paradimorphite corresponds to the high temperature polymorph of As4S3, whose existence was supposed by Arcangelo Scacchi in 1850 in the fumaroles at the Solfatara di Pozzuoli, Campi Flegrei, near Napoli, Italy.

Crystals of paradimorphite are orange yellow, transparent or semitransparent, with adamantine lustre. Habit is prismatic and observed forms are {110}, {101}, {111}, {100}, {010} and {001}. Tenacity is brittle, no distinct cleavage is observed and fracture is conchoidal. The mineral does not fluoresce in long- or shortwave ultraviolet light. No twinning is apparent. The streak is saffron yellow. Hardness (Mohs) = 1–2. The observed density is 3.510(3) g/cm3, calculated density is 3.500 g/cm3. The mineral is orthorhombic, space group Pnma, with a = 9.1577(7), b = 8.0332(6), c = 10.2005(8) Å, V = 750.41(10) Å3 and Z = 4. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 6.299(48)(011), 5.186(100)(111), 4.174(31)(201), 3.133(34)(022), 3.116(58)(212), 2.980(41)(122), 1.846 (27)(413) and 1.808(23)(134). The structure was refined to R = 0.0229 for 979 reflections with I >2σ(I). Crystals of paradimorphite contain As4S3 molecules, of idealised C3v symmetry, with the four arsenic atoms in a triangular pyramidal arrangement, with sulfur atom bridges on the three adjacent apical edges. Molecular dimensions and conformation are identical within standard uncertainties with those of the low-temperature polymorph dimorphite. No substantial differences, neither in the molecular packing nor in the molecular orientation, could be observed; minor differences being related to intermolecular distances only.

The new mineral, illoqite-(Ce), with the ideal formula Na2NaBaCeZnSi6O17, has been discovered in the Taseq Slope, Ilímaussaq Alkaline Complex, Southern Greenland. Illoqite-(Ce) occurs in a hyperalkaline ussingite vein closely related to one of the largest ussingite veins in the Ilímaussaq complex. The associated minerals are aegirine, arfvedsonite, a britholite-group mineral, epistolite, chkalovite, lueshite, Mn-rich pectolite group member and steenstrupine-(Ce). Illoqite-(Ce) crystallises as either single euhedral crystals up to 150 μm in size or radiating aggregates consisting of a few or many crystals. The aggregates are up to 200 μm in diameter. Illoqite-(Ce) can occur as scattered small groups of crystals or aggregates, but sometimes they occur in high concentrations creating clusters or bands almost completely consisting of illoqite-(Ce). The empirical formula on the basis of 17 anions is Na2.00Na1.00(Ba0.59Sr0.32Ca0.04Na0.03)Σ0.98(Ce0.68La0.31Nd0.09Pr0.04)Σ1.12(Zn0.42Fe0.34Li0.14Mn0.09)Σ0.99Si5.97O17, with the simplified formula being Na2Na(Ba,Sr)(Ce,La,Nd)(Zn,Fe,Li)Si6O17. Illoqite-(Ce) exhibits sector zoning between elements Sr and Ba. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R1 = 2.46% using 1902 unique reflections. Illoqite-(Ce) is orthorhombic, Pcca, with a = 14.5340(7), b = 5.2213(1), c = 19.8270(4) Å, V = 1507.25(6) Å3 and Z = 4. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 7.266 (79) (200), 4.688 (44) (104), 4.241 (64) (210), 3.486 (79) (114), 3.340 (52) (312), 2.986 (67) (410), 2.882 (100) (314) and 2.789 (44) (016). Illoqite-(Ce) is a new member of the nordite supergroup and is named after the Greenlandic word illoq, meaning cousin, in allusion to the mineral's close relation to nordite-(Ce).

Kaznakhtite, ideally Ni6Co3+2(CO3)(OH)16⋅4H2O, is a new member of the hydrotalcite group within the hydrotalcite supergroup. The mineral was discovered at the Kaznakhtinskiy ultrabasic massif, Altai Republic, SW Siberia, Russia. It occurs as powdery aggregates forming flattened lenses up to 1.5 × 0.5 cm and veinlets up to 1 cm long and up to 1 mm thick in aggregates of chrysotile, lizardite, stichtite and dolomite. Other associated minerals include brucite, chromite, heazlewoodite, manganochromite, magnetite and magnesioferrite. Kaznakhtite aggregates are composed of tiny platy grains up to 0.01 mm across. Kaznakhtite is light green and translucent in aggregates. It has an earthy lustre and white streak. Cleavage is micaceous on {001}. Dcalc = 2.864 g cm–3. The mineral is optically uniaxial (–) with ɛ = 1.657(3) and ω = 1.676(3), and weakly pleochroic in greenish hues, ω > ɛ. Chemical composition (wt.%, electron microprobe, Co valence state determined by XANES spectroscopy, CO2 and H2O calculated by stoichiometry) is: MgO 2.15, NiO 47.40, ZnO 0.22, Al2O3 0.16, Cr2O3 0.98, Co2O3 17.42, Cl 0.63, CO2 5.05, H2O 24.60, –O=Cl –0.14, total 98.47. The empirical formula calculated based on the sum of all metal cations = 8 apfu is (Ni5.54Mg0.47Zn0.02)Σ6.03(Co3+1.83Cr0.11Al0.03)Σ1.97C1.00O2.99(OH)15.84Cl0.16⋅4H2O. Infrared spectroscopy confirmed the presence of CO32– anions, OH– groups and H2O molecules. The crystal structure was refined by the Rietveld method with RB = 0.19%. Kaznakhtite is trigonal, space group R͞3m, a = 3.0515 (3), c = 23.180 (3) Å, V = 186.93 (4) Å3 and Z = 3/8. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 7.72 (100) (003); 3.863 (24) (006); 2.630 (4) (101); 2.576 (10) (012); 2.294 (6) (015); 1.950 (4) (018); 1.526 (4) (110); and 1.497 (4) (113). Kaznakhtite is a Co3+ analogue of reevesite, Ni6Fe3+2(CO3)(OH)16⋅4H2O. The mineral is named after its type locality.

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.

Kozłowskiite, ideally Ca4(Fe2+Sn3)(Si2O7)2(Si2O6OH)2, is a new mineral isostructural with kristiansenite and silesiaite, found as a band in the core of a zoned silesiaite–kristiansenite crystal from the granitic pegmatite at Szklarska Poręba, Lower Silesia, Poland. In tiny pieces kozłowskiite is pale brownish, with a calculated density of 3.775 g⋅cm–3 and a mean refractive index ~1.727. The triclinic crystal structure was determined with space-group symmetry C1: a = 10.0183(2), b = 8.3861(1), c = 13.3395(2) Å, α = 89.956(1), β = 109.039(2), γ = 89.979(1)° and V = 1059.40(3) Å3, although, similarly to kristiansenite, it is metrically monoclinic (Laue group 2/m) with α and γ angles equal to 90° and a = 10.0170(3), b = 8.3860(2), c = 13.3421(4) Å, β = 109.050(3)° and V = 1059.40(5) Å3. The seven strongest reflections in the calculated powder X-ray diffraction pattern are [d in Å (I) hkl]: 5.190 (73.2) 111, 1$\bar{1}$1; 4.569 (30.0) $\bar{2}$02; 3.153 (64.7) 004; 3.094 (28.1) $\bar{3}$11, $\bar{3}\bar{1}$1; 3.089 (100) $\bar{2}\bar{2}$2, $\bar{2}$22; 2.595 (27.2) 2$\bar{2}$2, 222; and 2.141 (30.6) $\bar{3}$31, $\bar{3}\bar{3}$1. Electron microprobe analysis gave (in wt.%) SiO2 39.46, ZrO2 0.35, SnO2 31.13, Al2O3 0.35, Sc2O3 2.65, total Fe as Fe2O3 5.06 (= Fe2O3calc. 2.26; FeOcalc. 2.52), MnO 0.71, CaO 18.42 and H2Ocalc. 1.48, sum 99.33. The empirical formula on the basis of 26O + 2(OH) and 16 cations (Z = 2) is Ca4.00(Sn2.52Sc0.47Fe2+0.43Fe3+0.34Mn2+0.12Al0.08Zr0.03)Σ4.00(Si2.00O7)2(Si2.00O6OH)2. The crystal structure of kozłowskiite was refined to an R1 = 2.12% for 4887 reflections with Io>2σI. The Ca and Si sites are occupied solely by Ca and Si, respectively, and three of four M sites: M2, M3 and M4, are dominated by Sn. Four hydrogen atoms present in the kozłowskiite unit cell are shared among the O17–O27 and O47–O37 oxygen atoms where O17 and O47 are OH groups forming relatively strong hydrogen bonds.