A new mineral cuprodobrovolskyite, ideally Na4Cu(SO4)3, was found in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with petrovite, saranchinaite, euchlorine, krasheninnikovite, langbeinite, calciolangbeinite, anhydrite, sanidine, tenorite and hematite. Cuprodobrovolskyite occurs as coarse hexagonal tabular or equant, typically skeletal crystals up to 1 mm and their clusters or crusts up to 1.5 cm × 2.5 cm in area. The mineral is transparent, light blue or greenish-bluish to almost colourless with vitreous lustre. Cuprodobrovolskyite is optically uniaxial (+) with ω = 1.509(3) and ε = 1.528(3). The empirical formula calculated on the basis of 12 O apfu is (Na3.64K0.09Pb0.03)Σ3.76(Cu0.51Ca0.22Mg0.16Zn0.07Al0.01Mn0.01)Σ0.98S3.04O12. The unit-cell parameters of cuprodobrovolskyite calculated from the powder X-ray diffraction data are: a = 15.702(2), c = 22.017(5) Å, V = 4701.0(2) Å3, space group R3 and Z = 18. The crystal structure was studied using the Rietveld method, Rp = 0.0246, Rwp = 0.0325, R1 = 0.0521 and wR2 = 0.0770. Cuprodobrovolskyite is an isostructural analogue of dobrovolskyite Na4Ca(SO4)3 with Cu prevailing over Ca. One of the main features of cuprodobrovolskyite is Cu2+ in 7-fold coordination. On the basis of relationships with saranchinaite Na2Cu(SO4)2 and petrovite Na12Cu2(SO4)8 in the Arsenatnaya fumarole and the results of heating experiments, cuprodobrovolskyite is considered as the highest-temperature phase among anhydrous Na–Cu sulfate minerals.

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