Volume 38 (2007): Issue 1 (June 2007)

Dovyrenite, simplified formula Ca₆Zr[Si₂O₇]₂(OH)₄, occurs as an accessory mineral in vein skarns developed in carbonate xenoliths in subvolcanic layered plagiodunite-troctolite series in the Ioko-Dovyren Massif of Proterozoic age, Northern Baikal Region, Buryatia, Russia. Dovyrenite is a late mineral of altered pyroxene and melilite-monticellite skarns. Associated minerals are Zr-bearing phases: fassaitic pyroxene, perovskite and hydrogarnets; and also monticellite, vesuvianite, diopside, foshagite, brucite, calzirtite, tazheranite, baghdadite, apatite, calcite, native bismuth, sphalerite, selenian galena, clausthalite, safflorite, rammelsbergite, pyrrhotite, pentlandite, valleriite, laitakarite, nickeline, nickel-skutterudite. The average structure of dovyrenite is orthorhombic, space group Pnnm, with subcell parameters A = 5.666(16) Å, B = 18.844(5) Å, C = 3.728(11) Å, V = 398.0(2) ų and Z = 1. Dovyrenite shows a new type of modular structure with stacking of the tobermorite-like and the rosenbuschite-like layers parallel to (010). Single-crystal structural data point to an incompletely occupied Ca(2) site from the rosenbuschite module which is confirmed by microprobe analyses: ZrO₂ 16.47, SiO₂ 32.83, TiO₂ 0.14, HfO₂ 0.16, Cr₂O₃ 0.01, CaO 43.87, FeO 0.25, MgO 0.13, MnO 0.02, Nb₂O₃ 0.03; total 99.38 wt% with calculated H₂O. The empirical formula is (Ca_5.73Fe_0.03Mg_0.02)_σ5.78(Zr_0.98Hf_0.01Ti_0.01)_σ1Si₄(O_13.56OH_0.44)_σ14(OH)₄. The presence of two types of OH group in the dovyrenite structure is corroborated by FTIR and Raman spectroscopy. Dovyrenite is an optically positive biaxial mineral: α 1.659(2), β 1.660(2); γ 1.676(2); 2Vz 30(5)° (measured), 28° (calculated). The coexistence of monticellite, foshagite and dovyrenite points to a narrow interval of crystallization 560-630°C under subvolcanic conditions (P < 10⁸ Pa).

Clinopyroxenites, phoscorites and carbonatites from the Devonian Seblyavr intrusion (Kola Peninsula, Russia) have petrographic characteristics indicating that they are accumulative in origin. Their geochemical (major and rare earth elements) compositions can be accounted for by mixtures of their major rock-forming minerals and accessory phases, i.e. they reflect the record of mineral accumulation. All of the analysed Seblyavr rocks are strongly LREE-enriched with (La/Yb)_N mostly ranging from 38 to 189. However, a dolomite carbonatite with hydrothermal LREE-Sr mineralization has an extreme (La/Yb)_N value of 1659. Such late-stage dolomite carbonatites were formed by hydrothermal (rather than magmatic) processes. Whole-rock samples of representative magmatic lithologies from Seblyavr have initial ⁸⁷Sr/⁸⁶Sr and ε_Nd that fall in a very narrow range from 0.7031 to 0.7033 and +4.9 to +5.9, respectively. We therefore conclude that clinopyroxenites, phoscorites and carbonatites were formed by differentiation and crystallization of a single batch of melt. The parental melt was derived from a depleted upper mantle source that had been meta-somatised prior to melting.

The experimental conversion of F-class fly ash into zeolites is described. The ash, composed mainly of aluminosilicate glass, mullite and quartz, was collected in the Cracow power plant (southern Poland). The experiments involved the heating of fly ash samples in PTFE vessels. Time, temperature and solution composition were the reaction parameters considered in the experiments and in the subsequent modeling. A series of reactions with 0.5, 3 and 5M NaOH solutions (and some with additional 3M NaCl) were carried out at 70°, 100° and 150°C for 12-48 hours under autogenic pressure (not measured) and at a constant ash-to-solution ratio of 33.3 g/l. The following zeolite phases were synthesized: sodalite (SOD structure), hydroxysodalite (SOD), CAN type phases, Na-X (FAU), and NaP1 (GIS). Statistically calculated relationships based on the mineral- and chemical compositions of the reaction products support the conclusion that the type of zeolite phase that crystallizes depends on the concentration of OH- and Cl- in solution and on the temperature of the reaction. The duration of reaction, if on the order of tens of hours, is of less significance. The nature of the zeolite phase that crystalises is controlled by the intensity and selectivity of the substrate dissolution. That dissolution can favour, in sequence, one or other of the components in the substrate, resulting in Si/Al variation in the reaction solutions. Mullite dissolution (decreasing solution Si/Al) characterizes the most advanced reaction stages. The sequence of crystallization of the zeolite phases mirrors the sequential dissolution of substrate components, and the composition of the crystallizing zeolite crystals reflects the changes in the solution Si/Al.

Samples from hydrothermal Sb-Au mineralization in the area SE of Nižná Boca village in the N&iAzke Tatry Mountains were investigated using a variety of geochemical and mineralogical methods. Ore minerals typically occur in N-S striking quartz-carbonate veins hosted by an I-type biotite granodiorite to tonalite of Variscan Age (the Ďumbier Type). Paragenetic associations in the deposit are comparable to other mineralizations of the same type in the Ďumbierske Nízke Tatry Mountains. A quartz-arsenopyrite, pyrite stage of mineralization is the oldest with a calculated temperature of formation of about 445°C. It is followed by a quartz-carbonate-stibnite, zinkenite stage and, in turn, a quartz-carbonate-sphalerite-galena, boulangerite-gold stage. The gold typically contains between 9-18 wt.% Ag regardless of mineral association. No evidence for further generations of gold was found although it is possible that some gold was remobilized from the structure of the auriferous arsenopyrite. The Au and Ag content of the bulk ore ranges from 0.53 g.t^-1 to 20.2 g.t^-1 and from 0.9 g.t^-1 to 31.2 g.t^-1, respectively. A tetrahedrite-chalcopyrite stage is followed by a barite-hematite stage - the youngest assemblage in the deposit. Fluid inclusions from the first mineralization stage are usually less than 3 μm in size and contain less than 3.6 wt.% CO₂; salinity, density and homogenization temperature range from 2.7-16.3 wt.% NaCl_(eq), 0.85-1.03 g.cm^-1 and 128-280°C, respectively.