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In this paper, we describe a unique occurrence of submicrometer polycrystalline zircon and arborescent aeschynite microcrystals on anatase with truncated bipyramidal habit, which were formed during low-temperature hydrothermal alteration of miarolitic cavities in a granophyre from Cuasso al Monte (Italy). The results suggest that temperatures in the range 100–250 °C and acidic conditions characterized the formation of anatase and that the preservation of this metastable phase was due to the presence of Nb (Nb/Ti atomic ratio ~0.032). We also detected an increase in the Nb content along the anatase rim. This is related to the incipient segregation of Nb driven by the transition toward the thermodynamically more stable rutile phase, which is possibly arrested by cooling below the diffusion blocking temperature. In these samples, zircon clearly postdates anatase and predates aeschynite. The resulting possible scenario is that F-rich hydrothermal fluids altered primary minerals at relatively high temperature and then, on cooling below 250 °C, deposited in the following sequence: anatase, zircon, and aeschynite, which reflects both elemental saturation and fluid fractionation with decreasing temperature. Finally, the aeschynite identified in this study through TEM-EDS shows an unusual chemical composition [(Fe0.35Ca0.22Th0.15U0.13Y0.10Pb0.11)Σ1.06(Nb1.05Ti0.69Al0.14As0.06)Σ1.94O6], which cannot be reconciled with any known aeschynite sub-species. Conventional classification suggests that it should be called niobioaeschynite-(Y), although Y is present at only 0.10 apfu, and Fe (0.35 apfu) predominates in the A-site. This suggests that the aeschynite-group mineral classification system should be re-considered.

We report about three bismuth sulfates from mineralized quartz dikes from Alfenza (Crodo, Italy), two new phases and a rare mineral, cannonite, all growing on bismuthinite. The first new phase occurs as white, “hortensia-like” aggregates of pseudo-hexagonal platelets, with perfect basal cleavage, ~20 μm wide and few micrometers thick. The approximate composition is Bi2O2(SO4), and cell parameters and symmetry, as determined by automatic diffraction tomography, are a = 22.0(4), b = 16.7(3), c = 15.9(3) Å, β = 102.9(5)°, space group Pc or P2/c. A major stacking disorder is detected by HR-SEM images and electron diffraction data.

AbstractWe report about three bismuth sulfates from mineralized quartz dikes from Alfenza (Crodo, Italy), two new phases and a rare mineral, cannonite, all growing on bismuthinite. The first new phase occurs as white, “hortensia-like” aggregates of pseudo-hexagonal platelets, with perfect basal cleavage, ~20 µm wide and few micrometers thick. The approximate composition is Bi2O2(SO4), and cell parameters and symmetry, as determined by automatic diffraction tomography, are a = 22.0(4), b = 16.7(3), c = 15.9(3) Å, ß = 102.9(5)°, space group Pc or P2/c. A major stacking disorder is detected by HR-SEM images and electron diffraction data. The second new phase was detected only by TEM. It can be distinguished by its random orientation on the TEM grid (i.e., absence of preferential parting), the higher resistance under the electron beam, and different cell parameters and structure, whereas the composition is similar (Bi/S ~2.2/1), apart for the presence of tellurium up to ~6 cations percents. The unit cell is hexagonal, space group P62c, a = 9.5(2) and c = 15.4(3) Å. In this case, a structure model was obtained ab initio from electron diffraction data. Interestingly, the mineral has a porous structure with one dimensional porosity (diameter of the channel ~7 Å). Finally, within the same centimeter sized hand-specimens, we detected also cannonite. Its identification was done by automatic diffraction tomography. The measured cell parameters are a = 7.7(2), b = 13.9(3), c = 5.7(1) Å, ß = 109.8(5)°, the space group P21/c. Cannonite at Alfenza forms radiating, acicular aggregates of colorless, transparent crystals with “scalpel-like” habit, elongated along c, up to 200 µm in length.

TiO2dispersed in polyester acrylate membranes was tested as a photocatalyst in the phenol mineralization reaction assisted by molecular oxygen. Kinetics experiments revealed that, although embedded, the oxide maintains significant catalytic activity. This result was first attributed to the homogeneous dispersion inside the polymeric host of TiO2nanocrystals, which can be easily irradiated and interact with the reactants. Furthermore, the investigation of the photogenerated charge carriers in the photocatalyst demonstrated that electrons are trapped on Ti3+centers, while holes are trapped on C-centered species of the polymer matrix. In the presence of O2, the C-centered radicals of the polymer transform into peroxy radicals, reinforcing the charge separation in the polymer-embedded oxide with respect to the powder. The positive interference of the polymer matrix in reinforcing the electron−hole separation is responsible for the relevant photoactivity of the embedded TiO2.