A new mineral kalithallite, K3Tl3+Cl6⋅2H2O, was found in an active fumarole belonging to the Northern fumarole field at the First scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Kalithallite is a product of the relatively low-temperature (70–150°C) interactions involving high-temperature sublimate minerals, volcanic gas and atmospheric water vapour. The associated minerals are cryobostryxite, KZnCl3⋅2H2O, halite, sylvite, opal and gypsum. Kalithallite forms lamellar to tabular crystals up to 5 × 30 × 40 μm combined in open-work aggregates up to 1 mm across. It is transparent, colourless in individuals and white to pale cream coloured or pale beige in aggregates, with vitreous lustre. Dcalc = 3.01 g cm–3. Kalithallite is optically uniaxial (–), ɛ = 1.656(3) and ω = 1.662(3). The chemical composition (wt.%, electron-microprobe data, H2O calculated by stoichiometry) is: K 17.72, Zn 0.85, Tl 38.76, Cl 35.91, H2Ocalc 5.99, total 99.23. The empirical formula calculated on the basis of K+Zn+Tl+Cl = 10 apfu is K2.72Zn0.06Tl1.14Cl6.08⋅2H2O. Kalithallite is tetragonal, I4/mmm, a = 15.9333(5), c = 18.1088(7) Å, V = 4595.2(4) Å3 and Z = 14. The strongest reflections of the powder X-ray diffraction (XRD) pattern [d,Å(I)(hkl)] are: 5.98(100)(202); 5.64(36)(220); 3.984(20)(400); 3.528(30)(224); 3.315(22)(422); 2.890(15)(334); and 2.817(24)(206, 440). Kalithallite is isotypical to synthetic K3Tl3+Cl6⋅2H2O. The crystal structure was refined from the powder XRD data using the Rietveld method, RBragg = 0.55%, Rp = 0.56%, and Rwp = 0.75%. The structure contains Tl3+Cl6 octahedra and K-centred polyhedra of three types: KCl8, KCl8(H2O) and KCl7(H2O)2. The mineral is named as a kalium–thallium ordered compound.

The new mineral antofagastaite, ideally Na2Ca(SO4)2·1.5H2O, was found in the oxidation zone of sulfide–quartz veins at the abandoned Coronel Manuel Rodríguez mine, Mejillones, Antofagasta Province, Antofagasta Region, Chile. It is associated with sideronatrite, metasideronatrite, aubertite, gypsum, ferrinatrite, glauberite, amarillite and an unidentified Fe phosphate. Antofagastaite occurs as prismatic crystals up to 0.5 mm × 1 mm × 5 mm, elongated along [010], typically combined in open-work aggregates up to 1 cm across. Antofagastaite is transparent and colourless, with vitreous lustre. It is brittle; the Mohs’ hardness is ca 3. Cleavage is distinct on (001). Dmeas. is 2.42(1) and Dcalc. is 2.465 g cm−3. Antofagastaite is optically biaxial (–), α = 1.489(2), β = 1.508(2), γ = 1.510(2) and 2Vmeas. = 40(10)°. The IR spectrum is reported. Chemical composition (wt.%, electron microprobe, H2O determined by gas chromatography) is: Na2O 20.85, CaO 17.42, SO3 52.56, H2O 7.93, total 98.76. The empirical formula (based on 8 O atoms belonging to sulfate anions per formula unit with all H belonging to H2O molecules) is Na2.06Ca0.95S2.01O8·1.35H2O. Antofagastaite is monoclinic, P21/m, a = 6.4596(4), b = 6.8703(5), c = 9.4685(7) Å, β = 104.580(4)°, V = 406.67(5) Å3 and Z = 2. The strongest reflections of the powder XRD pattern [d, Å (I, %) (hkl)] are: 9.17 (100) (001), 5.501 (57) (011), 3.437 (59) (020), 3.058 (43) (003), 2.918 (50) (2¯11), 2.795 (35) (013) and 2.753 (50) (121, 201). The crystal structure was solved based on single-crystal X-ray diffraction data, R1 = 5.71%. The structure of antofagastaite consists of ordered and disordered blocks and is related to syngenite K2Ca(SO4)2·H2O. Incorporation of additional H2O molecules in the syngenite-type structure results in disorder of the one of the two tetrahedral sulfate groups occurring in antofagastaite. In addition to the above-reported type material, antofagastaite together with syngenite and blödite occurs in the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia.

Efflorescences in the geothermal field of SE Melos, Greece, contain significant amounts of hydrated Al sulphate, alunogen, which could represent the Melian alumen exploited in Roman times and commended by Pliny. The efflorescences at subaerial fumaroles are explained as follows: Sulphur crystallizes on oxidation of H2S emanating from depth. Weathering produces sulphuric acid enhancing groundwater alteration of volcanic rocks. The high geothermal gradient and arid climate stimulate efflorescences. Salts are recycled during wet and dry weather leading to Al-enrichment on loss of Fe(II,III) and other cations. δ34S‰ V-CDT values for sulphur in fumarole sublimates, solfatara soils and ‘veins’ range from —0.3 to 6.4‰, mean 3.8‰ (n = 8) while Al, Ca and Mg-sulphates in diverse settings range from —4.1 to 6.8‰ (n = 16). The values for sulphur indicate that the initial H2S had an igneous source and the signature is largely inherited by the sulphates.

This study aims to underpin research into the exploitation of industrial minerals in the Roman period. When searching for early alumen workings, areas with evidence of acid sulphate alteration (white rocks) and sulphurous fumarole activity should be investigated.

A new mineral chrysothallite K6Cu6Tl3+Cl17(OH)4·H2O was found in two active fumaroles, Glavnaya Tenoritovaya and Pyatno, at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Chrysothallite seems to be a product of the interactions involving high-temperature sublimate minerals, fumarolic gas and atmospheric water vapour at temperatures not higher than 150ºC. It is associated with belloite, avdoninite, chlorothionite, sanguite, eriochalcite, mitscherlichite, sylvite, carnallite and kainite at Glavnaya Tenoritovaya and with belloite, avdoninite, chlorothionite, eriochalcite, atacamite, halite, kröhnkite, natrochalcite, gypsum and antlerite at Pyatno. The mineral forms equant-to-thick tabular crystals up to 0.05 mm, typically combined in clusters or crusts up to 1 mm across. Crystal forms are: {001}, {100}, {110}, {101} and {102}. Chrysothallite is transparent, bright golden-yellow to light yellow in finely crystalline aggregates. The lustre is vitreous. The mineral is brittle. Cleavage was not observed, the fracture is uneven. Dmeas = 2.95(2), Dcalc = 2.97 g cm–3. Chrysothallite is optically uniaxial (+), ω = 1.720(5), ε = 1.732(5). The Raman spectrum is given. The chemical composition (wt.%, electron-microprobe data, H2O calculated based on the crystal structure data) is: K 15.92, Cu 24.56, Zn 1.38, Tl 13.28, Cl 40.32, H2O(calc.) 3.49, total 98.95. The empirical formula, calculated on the basis of 17 Cl + 5 O a.p.f.u., is: K6.09(Cu5.78Zn0.32)Σ6.10Tl0.97Cl17[(OH)3.80O0.20]·H2O. Chrysothallite is tetragonal, I4/mmm, a = 11.3689(7), c = 26.207(2) Å, V = 3387.3(4) Å3, Z = 4. The strongest reflections of the powder X-ray pattern [d, Å (I)(hkl)] are: 13.20(44)(002); 6.88(100)(112); 5.16(30)(202, 114); 4.027(25)(220); 3.471(28)(206), 3.153(30)(314), 3.075(47)(305), 2.771(38)(316). The crystal structure (solved from single-crystal X-ray diffraction data, R = 0.0898) is unique. Its basic structural unit is a (001) layer of edge-sharing distorted CuCl4(OH)2 octahedra. Two Tl3+ cations occupy the centre of isolated TlCl6 and TlCl4(H2O)2 octahedra connected to each other and to the Cu polyhedral layers via KCl6 and KCl9 polyhedra. The name reflects the bright golden-yellow colour of the mineral (from the Greek χρυσος, gold) and the presence of thallium. Chrysothallite is the second known mineral with species-defining trivalent thallium.