Search

—In the $${\text{Cu}}_{3}^{{2 + }}$$ (T5+O4)2 (T = As, V or P) natural system arsenates are trimorphous (lammerite, lammerite-β, and unnamed triclinic Cu3[(As,V)O4]2), as well as vanadates (mcbirneyite, pseudolyonsite, and borisenkoite), while phosphates are represented by a poorly studied lammerite-like Cu3[(P,As)O4]2 phase. In active oxidizing-type fumaroles related to the Tolbachik volcano in Kamchatka, Russia, all these minerals crystallized at temperature no lower than 250°C. The crystal structure of natural triclinic Cu3[(As,V)O4]2 was first studied on a single crystal from the Yadovitaya fumarole at Tolbachik; R = 4.89%. It is isostructural to stranskiite and mcbirneyite and crystallizes in the P-1 space group; the unit-cell parameters are: a = 5.0701(8), b = 5.4047(8), c = 6.3910(8) A, α = 70.091(13), β = 86.828(12), γ = 68.399(15)°, V = 152.61(4) A3, and Z = 1. This paper also contains new data on mcbirneyite (its novel As-enriched variety is characterized), lammerite, and lammerite-β. Original and previously published materials on natural members of the Cu3(T5+O4)2 system are summarized and isomorphism and other crystal chemical features of minerals belonging to this system are discussed in comparison with the data on related synthetic compounds.

A new mineral, hilarionite, ideally Fe 2 3+ (SO4)(AsO4)(OH) · 6H2O, has been found in the Hilarion Mine, Agios Konstantinos, Kamariza, Lavrion district, Attiki Prefecture, Greece. It was formed in the oxidation zone of a sulfide-rich orebody in association with goethite, gypsum, bukovskyite, jarosite, melanterite, chalcanthite, allophane, and azurite. Hilarionite occurs as light green (typically with an olive or grayish tint) to light yellowish green spherulites (up to 1 mm in size) and bunches of prismatic to acicular “individuals” up to 0.5 mm long that are in fact near-parallel or divergent aggregates of very thin, curved fibers up to 0.3 mm long and usually lesser than 2 μm thick. The luster is silky to vitreous. The Mohs’ hardness is ca. 2. Hilarionite is ductile, its “individuals” are flexible and inelastic; fracture is uneven or splintery. D(meas) = 2.40(5), D(calc) = 2.486 g/cm3. IR spectrum shows the presence of arsenate and sulfate groups and H2O molecules in significant amounts. The Mossbauer spectrum indicates the presence of Fe3+ at two six-fold coordinated sites and the absence of Fe2+. Hilarionite is optically biaxial (+), α = 1.575(2), γ = 1.64(2), 2V is large. The chemical composition (electron microprobe, average of 7 point analyses; H2O determined by modified Penfield method) is as follows, wt %: 0.03 MnO, 0.18 CuO, 0.17 ZnO, 33.83 Fe2O3, 0.22 P2O5, 18.92 As2O5, 22.19 SO3, 26.3 H2O, total is 101.82%. The empirical formula calculated on the basis of 15 O is: (Fe 1.90 3+ Cu0.01Zn0.01)Σ1.92[(SO4)1.24(AsO4)0.74(PO4)0.01]Σ1.99(OH)1.01 · 6.03H2O. The X-ray powder diffraction data show close structural relationship of hilarionite and kaňkite, Fe 2 3+ (AsO4)2 · 7H2O. Hilarionite is monoclinic, space group C2/m, Cm or C2, a = 18.53(4), b = 17.43(3), c = 7.56(1) A, β = 94.06(15)°, V = 2436(3) A3, Z = 8. The strongest reflections in the X-ray powder diffraction pattern (d, A-I[hkl]) are: 12.66–100[110], $$7.60 - 6[00\bar 1]$$ , 5.00–10[22l], $$4.70 - 10[31\bar 1]$$ , 4.33–7[040]. Hilarionite is named after its type locality.

The crystal structures of cation-exchanged forms of hilairite obtained at 90°C (Pb- and Rb- exchanged samples (Pb0.60Na0.40H0.40ZrSi3O9 ∙ 3H2O [R32, a = 10.4718(3) A, c = 7.9392(2) A] and Rb1.48Na0.45H0.07ZrSi3O9 ∙ 0.53H2O[R3, a = 10.4743(4) A, c= 15.5433(8) A]) and at 150°C (K- and Cs-exchanged samples K1.81Na0.09H0.10ZrSi3O9 [R3, a = 10.3804(2) A, c = 14.9541(6) A] and Na1.14Cs0.55H0.31ZrSi3O9 ∙ 0.90H2O [R32, a = 10.5472(4) A, c = 15.8797(7) A]) were studied by X-ray dif- fraction. Their structures are based on a framework composed of helical chains [Si3O9]8 and isolated Zr octahedra. Relationships were found between the characteristics of exchange cations and the temperature of the ion exchange, on the one hand, and the compositional and structural features of the products, such as the type and degree of distortion of the framework and the concentration and arrangement of exchange cations and residual Na, and H2O molecules, on the other hand. The affinity of hilairite for extraframework cations in the ion exchange was shown to decrease in the order K → Rb → Pb → Ba → Sr → Ca → Cs.

The crystal structure of a Pb-exchanged form of zorite is studied by X-ray diffraction: Pb3.95(Ca0.1Sr0.05)[Ti(Ti0.80Nb0.20)4Si12O38(OH)] · 9.52H2O (sp. gr. Cmmm, R = 0.0530 for 680 independent reflections). The structure retains the mixed polyhedral framework of zorite, Na6[Ti(Ti,Nb)4(Si6O17)2(O,OH)5] · 11H2O. This framework is composed of xonotlite-like [Si6O17] ribbons linked to each other by columns of vertex-sharing (Ti,Nb)O6 octahedra and isolated TiO5 half-octahedra. Lead atoms in the Pb-exchanged form occupy one site, unlike Cs cations in the Cs-exchanged form of zorite, which are strongly disordered and partially occupy eight positions. The position of Pb2+ cations corresponds to the Na(2) position in the zorite structure, the Sr position in the Sr-exchanged form of ETS-4, and the K position in the K-exchanged form and is similar to the position of the water molecule W(3) in the structure of the Cs-exchanged form of zorite.

The crystal structures of K-and Cs-exchanged forms of zorite were studied by X-ray diffraction and IR spectroscopy: K4.75Na1.82[Ti(Ti0.79Nb0.20)4Si12O34(O,OH)5.2] × 10.62 H2O (sp. gr. Cmmm, R= 0.0481 for 516 independent reflections) and Cs4.34Na1.90[Ti(Ti0.80Nb0.18)4Si12O34(O,OH)5] × 5.37 H2O (sp. gr. Cmmm, R = 0.0285 for 621 independent reflections). Both structures retain the mixed polyhedral framework of zorite: Na6Ti(Ti,Nb)4(Si6O17)2(O,OH)5 × nH2O, where n ∼ 11. It is shown that the positions of the atoms located in the cavities of the frameworks of these compounds differ from those in the structures of zorite and its synthetic analogs.