Thermessaite-(NH4), ideally (NH4)2AlF3(SO4), is a new mineral found as a medium- to high-temperature (~250–300°C) fumarole encrustation at the rim of La Fossa crater, Vulcano, Aeolian Islands, Italy. The mineral deposited as aggregates of minute (<0.2 mm) sharp prismatic crystals on the surface of a pyroclastic breccia in association with thermessaite, sulfur, arcanite, mascagnite, and intermediate members of the arcanite–mascagnite series.

The new mineral is colourless to white, transparent, non-fluorescent, has a vitreous lustre, and a white streak. The calculated density is 2.185 g/cm3. Thermessaite-(NH4) is orthorhombic, space group Pbcn, with a = 11.3005(3) Å, b = 8.6125(3) Å, c = 6.8501(2) Å, V = 666.69(4) Å3 and Z = 4. The eight strongest reflections in the powder X-ray diffraction data [d in Å (I)(hkl)] are: 5.65 (100)(200), 4.84 (89)(111), 6.85 (74)(110), 3.06 (56)(112), 3.06 (53)(221), 3.08 (47)(311), 2.68 (28)(022) and 2.78 (26)(130). The average chemical composition, determined by quantitative SEM-EDS (N by difference), is (wt.%): K2O 3.38, Al2O3 25.35, SO3 36.58, F 26.12, (NH4)2O 22.47, O = F –11.00, total 102.90. The empirical chemical formula, calculated on the basis of 7 anions per formula unit, is [(NH4)1.85K0.15]Σ2.00Al1.06F2.94S0.98O3.06. The crystal structure, determined from single-crystal X-ray diffraction data [R(F) = 0.0367], is characterised by corner-sharing AlF4O2 octahedra which form [001] octahedral chains by sharing two trans fluoride atoms [Al–F2 = 1.8394(6) Å]. Non-bridging Al–F1 distances are shorter [1.756(1) Å]. The two trans oxygen atoms [Al–O = 1.920(2) Å] are from SO4 tetrahedra. NH4+ ions occur in layers parallel to (100) which alternate regularly with (100) layers containing ribbons of corner-sharing AlF4O2 octahedra and associated SO4 groups. The NH4+ ions are surrounded by five oxygen atoms and by four fluorine atoms. The mineral is named as the (NH4)-analogue of thermessaite, K2AlF3(SO4), and corresponds to an anthropogenic phase found in the burning Anna I coal dump of the Anna mine, Aachen, Germany. Both mineral and mineral name have been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA2011-077).

Leguernite, ideally Bi12.67O14(SO4)5, is a new mineral found in high-temperature fumarolic assemblages at La Fossa crater, Vulcano, Aeolian Islands, Italy. It occurs as aggregates of needleshaped crystals associated strictly with anglesite, balićžunićite and an unknown Bi sulfate. Leguernite is colourless to white, transparent, non-fluorescent, has a sub-adamantine lustre and a white streak. Electron microprobe data led to the chemical formula (on the basis of 34 anions p.f.u.) (Bi12.40Pb0.15)Σ=12.55S5.08O34. The calculated density is 7.375 g cm–3. A Raman spectrum collected on a single crystal of leguernite confirmed the anhydrous nature of the mineral.

Leguernite is monoclinic, space group P2, with a = 11.2486(11), b = 5.6568(6), c = 11.9139(10) Å , β = 99.177(7)º, V = 748.39(12) Å3 and Z = 1. The crystal structure is built up of Bi–O blocks of a fluorite-like structure with Bi12O14 composition separated by a single sulfate ion along [100] and by Bi(SO4)45– groups along [101]. It can also be described as composed of (001) layers with composition [Bi12O14(SO4)6+]n alternating with layers of composition [Bi(SO4)4]n5– along [001]. Leguernite shows significant similarities with the synthetic Bi14O16(SO4)5 compound.

The eight strongest reflections in the powder X-ray diffraction data [d in Å (I) (hkl)] are: 3.220 (100) (013), 3.100 (95) (11), 2.83 (30) (020), 2.931 (25) (302), 2.502 (25) (04), 2.035 (20) (322), 1.875 (20) (24) and 5.040 (15) (110).

The name is in honour of Franc¸ois “Fanfan” Le Guern (1942–2011), who was a very active volcanologist and specialist in volcanic gases and sublimates. Both the mineral and the mineral name have been approved by the IMA-CNMNC (2013–051).

Balićžunićite, ideally Bi2O(SO4)2, is a new mineral found as a high-temperature fumarole sublimate (T = 600°C) at La Fossa crater, Vulcano, Aeolian Islands, Italy. It occurs as aggregates of mm-sized prismatic and elongated crystals (∼50 μm across and up to 200 μm long) associated with anglesite, leguernite, one other potentially new Bi-oxysulfate mineral, lillianite, galenobismutite, bismoclite, Cd-rich sphalerite, wurtzite, pyrite and pyrrhotite. Balićžunićite is colourless to white or pale brown, transparent and non-fluorescent. It has a vitreous lustre and a white streak. Electron microprobe analysis gives the following average chemical composition (wt.%): Bi2O3 68.68 and SO3 23.73, total 92.41. The empirical chemical formula, calculated on the basis of 9 anions p.f.u., is Bi1.99S2O9. The calculated density is 5.911 g/cm3.

Balićžunićite is triclinic, space group P, with a 6.7386(3), b 11.1844(5), c 14.1754(7) Å, α 80.082(2)°, β 88.462(2)°, γ 89.517(2)°, V = 1052.01(8) Å3 and Z = 6. The six strongest reflections in the X-ray powder-diffraction data [d in Å(I) (hkl)] are: 3.146 (100) (033), 3.486 (21) (004), 3.409 (12) (01), 3.366 (7) (200), 5.562 (4) (11), 5.433 (4) (111). Balićžunićite is the natural analogue of the stable low-temperature a form of synthetic Bi2O(SO4)2. The name is in honour of Tonci Balić-Žunić(born 1952), Professor of Mineralogy at the Natural History Museum of the University of Cophenagen. Both the mineral and the mineral name have been approved by the IMA-CNMNC Commission (IMA2012-098).