Fassinaite, Pb22+(S2O3)(CO3), the first mineral with coexisting thiosulphate and carbonate groups: description and crystal structure

Fassinaite, ideally Pb-2(2+)(S2O3)(CO3), is a new mineral from the Trentini mine, Mount Naro, Vicenza Province, Veneto, Italy (holotype locality). It is also reported from the Erasmus adit, Schwarzleo District, Leogang, Salzburg, Austria and the Friedrich-Christian mine, Schapbach, Black Forest, Baden-Wurttemberg, Germany (cotype localities). At the Italian type locality it occurs as acicular [010], colourless crystals up to 200 mu m long, closely associated with galena, quartz and anglesite. At the Austrian cotype locality it is associated with cerussite, rare sulphur and very rare phosgenite. At the German cotype locality anglesite is the only associated phase. Fassinaite crystals commonly have flat chisel-shaped terminations. They arc transparent with vitreous to adamantine lustre and a white streak. Fassinaite is brittle with an irregular fracture and no discernible cleavage; the estimated Mohs hardness is 1 1/2-2. The calculated density for the type material is 6.084 g cm(-3) (on the basis of the empirical formula), whereas the X-ray density is 5.947 g cm(-3). In common with other natural lead thiosulphates (i.e. sidpietersite and steverustite) fassinaite has intense internal reflections, which do not allow satisfactory optical data to be collected; the crystals arc length-slow and have very high birefringence. The mineral is not fluorescent. Fassinaite is orthorhombic, space group Pupa, with unit-cell parameters (for the holotype material) a = 16.320(2), b = 8.7616(6), c = 4.5809(7) angstrom, V = 655.0(1) angstrom(3), a:b:c = 1.863:1:0.523, Z = 4. Single-crystal structural studies were carried out on crystals from all three localities: R-1(F) values range between 0.0353 and 0.0596. The structure consists of rod-like arrangements of Pb-centred polyhedra that extend along the [010] direction. These 'rods' are linked, alternately, by (CO3)(2-) and (S2O3)(2-) groups. The (S2O3)(2-) groups point alternately left and right (in a projection on [001] with [010] set vertical) if the apex occupied by the S2- in the thiosulphate group is defined to be the atom giving the direction. The lead atoms are nine-coordinated by seven oxygen atoms and two sulphur (S2-) atoms. The eight strongest X-ray powder-diffraction lines [d in angstrom (I/I-0)(hkl)] are: 4.410 (39) (101), 4.381 (59) (020), 4.080 (62) (400), 3.504 (75) (301), 3.108 (100) (121), 2.986 (82) (420), 2.952 (49) (221) and 2.736 (60) (321). Electron-microprobe analyses produce an empirical formula Pb-2.01(1)(S1.82(2)O3)CO3 (on the basis of six oxygen atoms). The presence of both carbonate and thiosulphate groups was corroborated by Raman spectra, which are discussed in detail. Fassinaite is named after Bruno Fassina (b. 1943), an Italian mineral collector who discovered the mineral in 2009.