Khvorovite, Pb2+4Ca2[Si8B2(SiB)O28]F, a new hyalotekite-group mineral from the Darai-Pioz alkaline massif, Tajikistan: Description and crystal structure

Abstract

AbstractKhvorovite, ideally Pb42+Ca2[Si8B2(SiB)O28]F, is a new borosilicate mineral of the hyalotekite group from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, Tajikistan. Khvorovite was found in a pectolite aggregate in silexites (quartz-rich rocks). The pectolite aggregate consists mainly of pectolite, quartz and fluorite, with minor aegirine, polylithionite, turkestanite and baratovite; accessory minerals are calcite, pyrochlore-group minerals, reedmergnerite, stillwellite-(Ce), pekovite, zeravshanite, senkevichite, sokolovaite, mendeleevite-(Ce), alamosite, orlovite, leucosphenite and several unknown Cs-silicates. Khvorovite occurs as irregular grains, rarely with square or rectangular sections up to 150 μm, and grain aggregates up to 0.5 mm. Khvorovite is colourless, rarely white, transparent with a white streak, has a vitreous lustre and does not fluoresce under ultraviolet light. Cleavage and parting were not observed. Mohs hardness is 5–5.5, and khvorovite is brittle with an uneven fracture. The measured and calculated densities are 3.96(2) and 3.968 g/cm3, respectively. Khvorovite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.659(3), βcalc. = 1.671(2), γ = 1.676(3); 2Vmeas. = 64(3)°, medium dispersion: r < v. Khvorovite is triclinic, space group I1¯, a = 11.354(2), b = 10.960(2), c = 10.271(2) Å, α = 90.32(3), β = 90.00(3), γ = 90.00(3)°, V = 1278(1) Å3, Z = 2. The six strongest lines in the powder X-ray diffraction pattern [d (Å), I, (hkl)] are: 7.86, 100, (110); 7.65, 90, (101); 7.55, 90, (011); 3.81, 90, (202); 3.55, 90, (301); 2.934, 90, (312, 312). Chemical analysis by electron microprobe gave SiO2 36.98, B2O3 6.01, Y2O3 0.26, PbO 40.08, BaO 6.18, SrO 0.43, CaO 6.77, K2O 1.72, Na2O 0.41, F 0.88, O=F –0.37, sum 99.35 wt.%. The empirical formula based on 29 (O+F) a.p.f.u. is (Pb2.762+Ba0.62K0.56Na0.16)Σ4.10(Ca1.86Sr0.06Y0.04Na0.04)Σ2[Si8B2(Si1.46B0.65)Σ2.11O28](F0.71O0.29), Z = 2 , and the simplified formula is (Pb2+, Ba, K)4Ca2[Si8B2(Si,B)2O28]F. The crystal structure of khvorovite was refined to R1 = 2.89% based on 3680 observed reflections collected on a four-circle diffractometer with MoKα radiation. In the crystal structure of khvorovite, there are four [4]-coordinated Si sites occupied solely by Si with <Si–O>= 1.617 Å. The [4]-coordinated B site is occupied solely by B, with <B–O> = 1.478 Å. The [4]-coordinated T site is occupied by Si and B (Si1.46B0.54), with <T–O> = 1.605 Å; it ideally gives (SiB) a.p.f.u. The Si, B and T tetrahedra form an interrupted framework of ideal composition [Si8B2(SiB)O28]11–. The interstitial cations are Pb2+, Ba and K (minor Na) [A(11–22) sites] and Ca [M site]. The two A sites are each split into two subsites ∼0.5 Å apart and occupied by Pb2+ and Ba + K. The [8]-coordinated M site is occupied mainly by Ca, with minor Sr, Y and Na. Khvorovite is a Pb2+ analogue of hyalotekite, (Ba,Pb2+,K)4(Ca,Y)2[Si8(B,Be)2(Si,B)2O28]F and a Pb2+-, Ca-analogue of kapitsaite-(Y), (Ba,K)4(Y,Ca)2[Si8B2(B,Si)2O28]F. It is named after Pavel V. Khvorov (b. 1965), a Russian mineralogist, to honour his contribution to the study of the mineralogy of the Darai-Pioz massif.