Napoliite, Pb₂OFCl, a new mineral from Vesuvius volcano, and its relationship with dimorphous rumseyite

Abstract

Napoliite, ideally Pb2OFCl, is a new fluoroxychloride mineral found in a specimen from a fumarole formed subsequent to the 1944 eruption of Vesuvius volcano, Naples Province, Italy. It occurs as well-shaped lamellar crystals up to 0.25 × 0.25 × 0.01 mm typically forming clusters up to 0.4 × 0.4 mm on the surface of volcanic scoria in association with anglesite, artroeite, atacamite, calcioaravaipaite, cerussite, challacolloite, cotunnite, hephaistosite, manuelarossiite, matlockite and susannite. Napoliite is colourless with white streak and adamantine lustre. It is brittle and has a laminated fracture. Cleavage is perfect on {001}. Dcalc = 7.797 g cm–3. The calculated mean refractive index is 2.10. Chemical composition (wt.%, electron microprobe) is: PbO 91.71, F 3.89, Cl 7.34, –O=(F+Cl) –3.30, total 99.64. The empirical formula calculated on the basis of 3 anions is Pb1.999O0.997F0.996Cl1.007. Raman spectroscopy confirms the absence of OH– groups and H2O molecules in the mineral. Napoliite is tetragonal, space group P42/mcm, a = 5.7418(11), c = 12.524(4) Å, V = 412.9(2) Å3 and Z = 4. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 3.860 (85) (111); 3.139 (20) (004); 2.914 (100) (113); 2.866 (63) (200); 2.118 (19) (204); 2.027 (19) (220); 1.665 (20) (313); and 1.642 (23) (117). The crystal structure was refined to R1 = 0.024 for 222 reflections with F > 4σ(F). It is based on lead oxide blocks derived from that of litharge PbO, which alternate with layers of chloride ions. Napoliite represents a new structure type with a unique order/disorder pattern of fluorine and oxygen atoms. The new mineral is dimorphous with rumseyite. It is named after the city of Naples (Napoli in Italian).