In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Integration of zircon and apatite U–Pb geochronology and geochemical mapping of the Wude basalts(Emeishan large igneous province):A tool for a better understanding of the tectonothermal and geodynamic evolution of the Emeishan LIP

Radiogenic isotopic dating and Lu–Hf isotopic composition using laser ablation-inductively coupled plasma-mass spectrometry(LA-ICP-MS)of the Wude basalt in Yunnan province from the Emeishan large igneous province(ELIP)yielded timing of formation and post-eruption tectonothermal event.Holistic lithogeochemistry and elements mapping of basaltic rocks were further reevaluated to provide insights into crustal contamination and formation of the ELIP.A zircon U–Pb age of 251.3±2.0 Ma of the Wude basalt recorded the youngest volcanic eruption event and was consistent with the age span of 251-263 Ma for the emplacement of the ELIP.Such zircons hadε_Hf(t)values ranging from7.3 to+2.2,identical to those of magmatic zircons from the intrusive rocks of the ELIP,suggesting that crust-mantle interaction occurred during magmatic emplacement,or crust-mantle mixing existed in the deep source region prior to deep melting.The apatite U–Pb age at 53.6±3.4 Ma recorded an early Eocene magmatic superimposition of a regional tectonothermal event,corresponding to the Indian–Eurasian plate collision.Negative Nb,Ta,Ti and P anomalies of the Emeishan basalt may reflect crustal contamination.The uneven Nb/La and Th/Ta values distribution throughout the ELIP supported a mantle plume model origin.Therefore,the ELIP was formed as a result of a mantle plume which was later superimposed by a regional tectonothermal event attributed to the Indian–Eurasian plate collision during early Eocene.     

Biochemical alterations in juvenile carp (Cyprinus carpio) exposed to zinc: glutathione reductase as a target

The aim of this study was to investigate biochemical changes in juvenile carp (Cyprinus carpio) exposed to zinc chloride (10, 30 and 100 microM) for a period of 48 h. Zinc exposure caused a concentration-dependent reduction in glutathione reductase (GR) activity in gills, liver and brain. Gill glutathione S-transferase (GST) was reduced when animals were exposed to the highest concentration of 100 microM zinc. The phosphorylation of p38(MAPK) increased in the brain of fish exposed to zinc 100 microM, while phosphorylation of the extracellular signal-regulated protein kinase 1/2 (ERK1/2) and c-Jun N-terminal protein kinase 1/2 (JNK1/2) remained unchanged. Expression of proteins HSP60 and HSP70 were not affected by zinc exposure. Considering the significant concentration-dependent inhibition of GR in all tissues analyzed, this enzyme could be a potential biomarker of exposure to zinc, which has to be confirmed.     

Coastal and estuarine habitat mapping, using LIDAR height and intensity and multi-spectral imagery

The airborne laser scanning LIDAR (LIght Detection And Ranging) provides high-resolution Digital Terrain Models (DTM) that have been applied recently to the characterization, quantification and monitoring of coastal environments. This study assesses the contribution of LIDAR altimetry and intensity data, topographically-derived features (slope and aspect), and multi-spectral imagery (three visible and a near-infrared band), to map coastal habitats in the Bidasoa estuary and its adjacent coastal area (Basque Country, northern Spain). The performance of high-resolution data sources was individually and jointly tested, with the maximum likelihood algorithm classifier in a rocky shore and a wetland zone; thus, including some of the most extended Cantabrian Sea littoral habitats, within the Bay of Biscay. The results show that reliability of coastal habitat classification was more enhanced with LIDAR-based DTM, compared with the other data sources: slope, aspect, intensity or near-infrared band. The addition of the DTM, to the three visible bands, produced gains of between 10% and 27% in the agreement measures, between the mapped and validation data (i.e. mean producer's and user's accuracy) for the two test sites. Raw LIDAR intensity images are only of limited value here, since they appeared heterogeneous and speckled. However, the enhanced Lee smoothing filter, applied to the LIDAR intensity, improved the overall accuracy measurements of the habitat classification, especially in the wetland zone; here, there were gains up to 7.9% in mean producer's and 11.6% in mean user's accuracy. This suggests that LIDAR can be useful for habitat mapping, when few data sources are available. The synergy between the LIDAR data, with multi-spectral bands, produced high accurate classifications (mean producer's accuracy: 92% for the 16 rocky habitats and 88% for the 11 wetland habitats). Fusion of the data enabled discrimination of intertidal communities, such as Corallina elongata, barnacles (Chthamalus spp.), and stands of Spartina alterniflora and Phragmites australis, which presented misclassification when conventional visible bands were used alone. All of these results were corroborated by the kappa coefficient of agreement. The high classification accuracy found here, selecting data sources, highlights the value of integrating LIDAR data with multi-spectral imagery for habitat mapping in the intertidal complex fringe.     

Prototype measurements and small-scale model tests of wave overtopping at shallow rubble-mound breakwaters: the Ostia-Rome yacht harbour case

The paper presents the comparison between the results of small-scale model tests and prototype measurements of wave overtopping at a rubble-mound breakwater. The specific structure investigated is the west breakwater of the yacht harbour of Rome at Ostia (Italy) and is characterized by a gentle seaward slope (1/4) and by a long, shallow foreshore. The laboratory tests firstly aimed at carefully reproducing two measured storms in which overtopping occurred and was measured. The tests have been carried out in two independent laboratories, in a wave flume and in a wave basin, hence using a two-dimensional (2-D) and a three-dimensional (3-D) setup. In the 2-D laboratory tests no overtopping occurred during the storm reproductions; in the 3-D case discharges five to ten times smaller than those observed in prototype have been measured. This indicates the existence of model and scale effects. These effects have been discussed on the basis of the results of several parametric tests, which have been carried out in both laboratories, in addition to the storm reproductions, varying wave and water level characteristics. Final comparison of all the performed tests with 86 prototype measurements still suggests the existence of scale and model effects that induce strong underestimation of overtopping discharge at small scale. The scale reproduction of wave breaking on the foreshore, together with the 3-D features of the prototype conditions and the absence of wind stress in the laboratory measurements, have been individuated as the main sources of scale and model effects. The paper also provides a comparison between the data and a largely used formula for wave overtopping discharges in the presence of structures similar to the one at hand. The suitable value of a roughness factor that appears in that formula is investigated and good agreement is found with other recent researches on rubble-mound breakwaters.     

Dissolution mechanisms of silicate minerals yielded by intercomparison with glasses and radiation damage studies

The behaviour of two silicates (albite and olivine) toward aqueous dissolution has been investigated with emphasis to two aspects: (1) similarities and differences with silicate glasses; and (2) influence of ion bombardment which transforms the initially crystalline structure to a glass-like one. The occurrence on leached materials of hydrated layers enriched with metallic elements is checked by using high-energy ion beam analytical techniques.

It is shown that for both amorphous and crystalline silicates, dissolution involves competing processes responsible for either hydrated-layer generation (hydration by ion exchange and/or water permeation), or its destruction (hydrolysis of siloxane bonds and detachment of silica units). At moderate temperature ( 100°C), the latter processes dominate for crystalline silicates and the resulting dissolution is congruent. However, these silicates tend to behave like glasses upon ion bombardment above a critical dose. At higher temperature (> 200°C), hydration is markedly enhanced and thick altered layers are generated even on undamaged minerals such as albite and orthoclase, where alkali cations are easily exchangeable.     

Temperature,composition, and f O2 effects on intersite distribution of Mg and Fe2+ in olivines

Single-crystal X-ray structure refinement of natural olivines equilibrated at high temperature under controlled oxygen fugacity (f _O2) conditions, coupled with a structure-energy model were used to establish the influence of T, f _O2 and bulk chemistry on intracrystalline disorder.The results are: 1) The k _D (k _D = [(Fe M1·Mg M2)/(Fe M2·Mg M1)]) factor describing site population on M1, M2 polyhedra increases from values lower than 1 at T below 400–600° C (depending on composition) to values higher than 1 at higher temperature. 2) The increase of k _D with T is quite regular. 3) At constant temperature and pressure, k _D increases with increasing fayalite content in the mixture; 4) Contrary to previous observations (Will and Nover 1979; Nover and Will 1981) varying f _O2, within the stability range of the substance, has a negligible influence on intracrystalline disorder. 5) As ancillary results, the model confirms the defect scheme of Nakamura and Schmalzried (1983) for the investigated solids. Moreover, it shows that cationic vacancies are always created on M 1 site at the expense of Mg ions, while trivalent iron is always stabilized on M2 site. This explains the marked anisotropies observed in Fe-Mg interdiffusion (Buening and Busek 1973; Misener 1974; Schock et al. 1989).