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Please clickhereto download the map associated with this article. The late Miocene-Pliocene sedimentary fill of the Siena Basin (Tuscany, Italy) consists dominantly of clastics and has internal architecture that reflects the interplay of tectonics, relative sea-level changes and climate variations. Pliocene sediments are extensively exposed and overlay both late Miocene deposits and pre-Neogene bedrock. Specifically, Pliocene basin margin sediments consist largely of sand with gravel and mud intercalations, deposited mainly in nearshore settings with minor fluvial depositional episodes. They grade basinward to dominantly offshore fines with intervening turbiditic sand bodies. New fieldwork revealed that basin margin deposits, notwithstanding lithologically rather homogeneous, are made of a variety of sedimentary facies and bear several unconformities. They have been traditionally described and mapped using lithostratigraphic criteria, that have proven to be unfit to represent such complex stratigraphic architectures. The aim of this paper is to describe the allostratigraphic architecture of the Pliocene deposits exposed in a marginal key-area (45 km) of the northern Siena Basin by means of a 1:10,000 scale geological map. The recognized succession of allostratigraphic units and their bounding discontinuities, along with new biostratigraphic data from calcareous plankton, provides new insights into the geological history of the Siena Basin and represents valuable constraints for long-distance correlation. [ABSTRACT FROM PUBLISHER]

The performances of a gas-solid two-dimensional fluidized bed reactor in photocatalytic selective oxidation reactions, irradiated with traditional UV lamps or with a microscale illumination system based on UV emitting diodes (UVA-LEDs), have been compared. In the photocatalytic oxidative dehydrogenation of cyclohexane to benzene on MoOx/TiO2-A12O3 catalyst the use of UVA-LEDs modules allowed to achieve a cyclohexane conversion and benzene yield higher than those obtained with traditional UV lamps. The better performances with UVA-LEDs are due to the UVA-LEDs small dimensions and small-angle emittance, which allow photons beam be directed towards the photoreactor windows, reducing the dispersion outside of photoreactor or the optical path length. As a consequence, the effectively illuminated mass of catalyst is greater. We have found that this illumination system is efficient for photo-oxidative dehydrogenation of cyclohexane to cyclohexene on sulphated MoOx/γ-A12O3 and ethanol to acetaldehyde on VOx/TiO2. [ABSTRACT FROM AUTHOR]

Abstract: Tuscany (Central Italy) is a key area for studying the Messinian Salinity Crisis and overlying Lower Pliocene deposits due to the high number and excellence of the outcrops. Although the Miocene/Pliocene transition is well exposed and suitable for detailed analyses, a high-resolution integrated stratigraphic study of such a crucial time span for the geological history of the Mediterranean has never been attempted. In the Fine Basin (Central Tuscany), the Cava Serredi section is one of the best exposures of the upper Messinian–Lower Pliocene transition of the Northern Apennines. The Miocene/Pliocene boundary corresponds to a surface separating thinly laminated lacustrine (“Lago-Mare”) marls from homogeneous circalittoral to upper bathyal marly clays. Detailed quantitative micropalaeontological analyses have been performed on 111 samples from the 22m-thick Lower Pliocene succession. They resulted in the improvement of the biostratigraphic resolution of the basal Zanclean interval due to the recognition of several chronologically constrained bioevents typical of the Mediterranean region and based on benthic and planktonic foraminifera and calcareous nannofossils. Moreover, to unravel cyclical patterns of deposition, and given that the investigated succession shows no evident lithological pattern, micropalaeontological analyses have been coupled with calcium carbonate content variations. The latter revealed more-regular fluctuations, which are especially evident if the exclusive contribution of the planktonic foraminifer fraction (PCaCO3) is considered. Spectral analysis of the CaCO3 curve indicates that sedimentation occurred under the control of Earth''s precession. This datum is also confirmed by the cyclical patterns of Neogloboquadrina acostaensis and Sphenolithus spp. among foraminifers and nannofossils, respectively. According to the proposed cyclostratigraphic and astrochronological reconstruction, the Lower Pliocene interval of the Cava Serredi section consists of eight precession-controlled cycles ranging from the i-cycle 510 (5.33Ma) to the i-cycle 494 (5.16Ma). Finally, the comparison with other astronomically calibrated sections, including the Zanclean GSSP (Eraclea Minoa, Sicily), allowed us to prove the completeness of the basal Zanclean interval of the study section and to state that Pliocene re-flooding after the Messinian Salinity Crisis occurred synchronously with respect to other deeper sectors of the Mediterranean Basin. [Copyright &y& Elsevier]

Abstract: The photocatalytic oxidative dehydrogenation of cyclohexane on sulphated MoO x /γ-Al2O3 catalysts has been studied in a two-dimensional fluidized bed photoreactor. The influence of Mo loading at similar sulphate content and the effect of catalyst preparation method have been investigated. Considering the influence of Mo loading at similar sulphate content, the highest photoactivity at 2.4 SO4 wt% was found at MoO3 loading of 8wt%. Selectivity to cyclohexene was 100%, irrespective of the Mo content. At fixed MoO x content, in particular at 50% of theoretical monolayer coverage, the preparation method of catalysts strongly affected the photocatalysts performances, showing in addition a slight decrease in selectivity to cyclohexene due to side-production of benzene. All the catalysts showed a similar equivalent band gap energy. Thermogravimetric analysis evidenced the presence of surface sulphate species of different thermal stabilities. A linear correlation of photoactivity with the surface sulphates amount of lower thermal stability has been found for all sub-monolayer MoO x sulphated catalysts. The neighboring of surface sulphates to octahedral polymolybdate species appears to be a key parameter for the photoactivity of the catalysts. The catalyst selectivity was related to surface acidity. Higher acidity resulted in increased cyclohexene dark adsorption and consequently in enhanced benzene formation. [Copyright &y& Elsevier]