A Fe K-edge XAS study of amethyst

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.     

Lateral variations in tectonic style across cross-strike discontinuities: an example from the Central Apennines belt (Italy)

In foreland thrust belts, abrupt lateral changes in tectonic style, structural–stratigraphic features, and topography usually occur across cross-strike faults. The Central Apennines of Italy offer an exceptional scenario of lateral variations in tectonic setting. Here, the Sangro Volturno oblique thrust ramp (SVOTR) represents the outer thrust front of the Pliocene–Quaternary foreland thrust system, confining southward the axial culmination of the orogen that occurs in the Central Apennines. We present an interpretation of the Pliocene–Quaternary evolution of this cross-strike fault through an integrated dataset including structural-geological mapping and subsurface onshore seismic reflection profiles. The interpretation of the structural framework is augmented by the analysis of low-temperature thermochronometers from 32 new sites extending across the subsurface transverse structure. As evidenced by seismic line interpretation, the localization and development of the SVOTR have been influenced by inherited extensional faults within a positive inversion tectonics context. The regional distribution of the maximum paleotemperature values across the SVOTR constrains the original extent of the allochthonous thrust sheet over all its hanging-wall and footwall blocks. The Pliocene–Quaternary thrusting and inversion of SVOTR caused the strong hanging-wall uplift, which brought to the complete erosion of the allochthonous units and the exhumation of the Adria units. The integrated analysis of low-temperature thermochronometers and structural evidence as applied in the study case can define the role of major cross-strike discontinuities in foreland thrust belts, by constraining and verifying their tectonics inversion significance and the amount of related exhumation.     

Spatial modelling and uncertainty assessment of pyroclastic cover thickness in the Sorrento Peninsula

Assessing spatial variability of soil thickness is a critical issue for understanding and predicting slope processes. The present work was aimed at estimating the spatial scales at which the variation of pyroclastic cover thickness occurs in a sample area in the Sorrento Peninsula (Italy). Stochastic simulation was used to understand the spatial variability of pyroclastic cover thickness on Mount Pendolo and to assess its spatial uncertainty. In the study area, covering about 0.7 km², thickness measurements were collected using electrical resistivity tomography profiles, continuous core drillings and steel rod penetrometric tests. Variographic analysis revealed the occurrence of an anisotropic behaviour along the N50 and N140 directions. In the latter anisotropic direction, a nested variogram was fitted including (1) a long-range component which could be related to large-scale factors, like the curvature of the slope and contributing area and (2) a shorter scale variation which is probably associated with the occurrence of denudation processes or to the articulate cover/bedrock interface. To assess the spatial variability and uncertainty of pyroclastic cover thickness, a stochastic simulation algorithm was used and 500 equally probable images of cover thickness were yielded. The results showed that a better thickness distribution map can be drawn by simulating the data collected on the slope and at the footslope separately. The approach also allowed delineating the areas characterized by greater uncertainty, suggesting supplementary measurements to further improve the cover thickness distribution model, thus reducing the uncertainty.     

Tertiary age and paleostructural inferences of the eclogitic imprint in the Austroalpine outliers and Zermatt–Saas ophiolite, western Alps

The Austroalpine Sesia-Lanzo inlier and upper Austroalpine Dent Blanche, Mt. Mary and Pillonet outliers occur on top of the western-Alpine orogenic wedge and, as a whole, override the structurally composite ophiolitic Piemonte zone. Instead, the Mt. Emilius, Glacier-Rafray, Etirol-Levaz and other lower Austroalpine eclogitic outliers are inserted within the Piemonte zone, between its upper (Combin) and lower (Zermatt-Saas) tectonic elements, or within the latter. Rb-Sr dating on phengitic micas show that the eclogitic imprint in the lower Austroalpine outliers, conventionally regarded as Late Cretaceous by comparison with the Sesia-Lanzo inlier, is of Eocene age (49-40 Ma), like the underlying Zermatt-Saas ophiolite (45-42 Ma) between the Aosta valley and Gran Paradiso massif. ⁴⁰Ar-³⁹Ar plateau ages on the same mica concentrates of the ophiolitic Zermatt-Saas nappe (46-43 Ma) are consistent with Rb-Sr dating, whereas that on the Austroalpine Glacier-Rafray klippe (92 Ma) is influenced by argon excess. The lower Austroalpine outliers underwent the subduction metamorphism concurrently with the Zermatt-Saas nappe, 20-25 Ma later than the eclogitic Sesia-Lanzo inlier and blueschist Pillonet klippe. The temporal gap and present intra-ophiolitic position mean that the lower Austroalpine outliers were probably derived from an intraoceanic extensional allochthon (Mt. Emilius domain) stranded inside the Piemonte-Ligurian ocean far from the Dent Blanche-Sesia domain and Adriatic margin.     

Microbial photosynthesis in coral reef sediments (Heron Reef, Australia)

We investigated microphytobenthic photosynthesis at four stations in the coral reef sediments at Heron Reef, Australia. The microphytobenthos was dominated by diatoms, dinoflagellates and cyanobacteria, as indicated by biomarker pigment analysis. Conspicuous algae firmly attached to the sand grains (ca. 100 μm in diameter, surrounded by a hard transparent wall) were rich in peridinin, a marker pigment for dinoflagellates, but also showed a high diversity based on cyanobacterial 16S rDNA gene sequence analysis. Specimens of these algae that were buried below the photic zone exhibited an unexpected stimulation of respiration by light, resulting in an increase of local oxygen concentrations upon darkening. Net photosynthesis of the sediments varied between 1.9 and 8.5 mmol O₂ m⁻² h⁻¹ and was strongly correlated with Chl a content, which lay between 31 and 84 mg m⁻². An estimate based on our spatially limited dataset indicates that the microphytobenthic production for the entire reef is in the order of magnitude of the production estimated for corals. Photosynthesis stimulated calcification at all investigated sites (0.2–1.0 mmol Ca²⁺ m⁻² h⁻¹). The sediments of at least three stations were net calcifying. Sedimentary N₂-fixation rates (measured by acetylene reduction assays at two sites) ranged between 0.9 to 3.9 mmol N₂ m⁻² h⁻¹ and were highest in the light, indicating the importance of heterocystous cyanobacteria. In coral fingers no N₂-fixation was measurable, which stresses the importance of the sediment compartment for reef nitrogen cycling.