X-ray absorption study of Ti-bearing silicate glasses

Ti K-edge XANES spectra have been collected on a series of Ti-bearing silicate glasses with metasilicate and tetrasilicate compositions. The intensity of the preedge feature in these spectra has been found to change with glass composition and varies from 29 to 58% (normalized intensity) suggesting a variation in structural environent around the absorbing atom. The pre-edge peak intensity increases for the alkali titanium tetrasilicate glasses from 35% to 58% in the order Li < Na < K < Rb, Cs whereas for the metasilicate compositions there is a maximum for the K-bearing glass. The pre-edge peak intensity remains constant for the alkaline earth titanium metasilicate glasses, Ca and Sr (34%) but increases slightly for Ba (41%). As the intensity of this feature is inversely correlated with coordination number, a comparison of the pre-edge intensity data for the investigated glasses with those of materials of known coordination number leads us to establish a regression equation and to infer that the average coordination number of Ti in these glasses ranges from 4.8 to 5.8. Large alkali cations appear to stabilize a relatively low average coordination number for Ti in silicate melts. The Ti structural environment results appear also to vary as a function of SiO₂ content within the K₂O-TiO₂-SiO₂ system. A number of physical properties of the melts from which these glasses were quenched and of other Ti-bearing silicate melts, have been determined in recent years. Clear evidence of a variable coordination number of Ti, consistent with the interpretation of the present XANES data is available from density measurements. These and other property determinations are compared with the present spectroscopic observations in an attempt to relate structure and properties in these melts which contain a major component with variable coordination number.     

Diagenetic controls on the isotopic composition of carbonate‐associated sulphate in the Permian Capitan Reef Complex,West Texas

Late Palaeozoic‐age strata from the Capitan Reef in west Texas show facies‐dependent heterogeneity in the sulphur isotopic composition of carbonate‐associated sulphate, which is trace sulphate incorporated into carbonate minerals that is often used to reconstruct the sulphur isotopic composition of ancient seawater. However, diagenetic pore fluid processes may influence the sulphur isotopic composition of carbonate‐associated sulphate. These processes variously modify the sulphur isotopic composition of incorporated sulphate from syndepositional seawater in shelf crest, outer shelf, shelf margin and slope depositional settings. This study used a new multicollector inductively‐coupled plasma mass spectrometry technique to determine the sulphur isotopic composition of samples of individual depositional and diagenetic textures. Carbonate rocks representing peritidal facies in the Yates and Tansill formations preserve the sulphur isotopic composition of Guadalupian seawater sulphate despite alteration of the carbon and oxygen isotopic compositions by meteoric and dolomitizing diagenetic processes. However, sulphur isotopic data indicate that limestones deposited in reef and slope facies in the Capitan and Bell Canyon formations largely incorporate sulphate from anoxic marine‐phreatic pore fluids isotopically modified from seawater by microbial sulphate reduction, despite generally preserving the carbon and oxygen isotopic compositions of Permian seawater. Some early and all late meteoric calcite cements have carbonate‐associated sulphate with a sulphur isotopic composition distinct from that of Permian seawater. Detailed petrographic and sedimentary context for carbonate‐associated sulphate analyses will allow for improved reconstructions of ancient seawater composition and diagenetic conditions in ancient carbonate platforms. The results of this study indicate that carbonate rocks that diagenetically stabilize in high‐energy environments without pore fluid sulphate gradients can provide a robust archive of ancient seawater's sulphur isotopic composition.     

Understanding the collapse–eruption link at Stromboli,Italy: A microanalytical study on the products of the recent Secche di Lazzaro phreatomagmatic activity

The Secche di Lazzaro (SDL) phreatomagmatic activity, with the associated Neostromboli sector collapse, represents the most powerful activity of the last 6 ky at Stromboli. As revealed by its present-day activity, Stromboli is one of the most eruptive volcanoes in Italy, and flank instability, along its NW flank, is a common process. Volcano instability is often dramatised by explosive eruptions, thus it is of crucial importance to understand the linking between volcano collapse and the plumbing system itself. The possible role of pre-eruptive magmatic processes as triggers of explosive eruptions can be mainly preserved by minerals and revealed by petrochemical studies. We studied the juvenile components (scoria and pumice) of the pyroclastic deposits from the SDL phreatomagmatic activity with the aim to understand the eruption–collapse link.     

Inverse differentiation pathway by multiple mafic magma refilling in the last magmatic activity of Nisyros Volcano, Greece

Based on detailed field, petrographic, chemical, and isotopic data, this paper shows that the youngest magmas of the active Nisyros volcano (South Aegean Arc, Greece) are an example of transition from rhyolitic to less evolved magmas by multiple refilling with mafic melts, triggering complex magma interaction processes. The final magmatic activity of Nisyros was characterized by sub-Plinian caldera-forming eruption (40?ka), emplacing the Upper Pumice (UP) rhyolitic deposits, followed by the extrusion of rhyodacitic post-caldera domes (about 31–10?ka). The latter are rich in magmatic enclaves with textural and compositional (basaltic–andesite to andesite) characteristics that reveal they are quenched portions of mafic magmas included in a cooler more evolved melt. Dome-lavas have different chemical, isotopic, and mineralogical characteristics from the enclaves. The latter have lower ⁸⁷Sr/⁸⁶Sr and higher ¹⁴³Nd/¹⁴⁴Nd values than dome-lavas. Silica contents and ⁸⁷Sr/⁸⁶Sr values decrease with time among dome-lavas and enclaves. Micro-scale mingling processes caused by enclave crumbling and by widespread mineral exchanges increase from the oldest to the youngest domes, together with enclave content. We demonstrate that the dome-lavas are multi-component magmas formed by progressive mingling/mixing processes between a rhyolitic component (post-UP) and the enclave-forming mafic magmas refilling the felsic reservoir (from 15?wt.% to 40?wt.% of mafic component with time). We recognize that only the more evolved enclave magmas contribute to this process, in which recycling of cumulate plagioclase crystals is also involved. The post-UP end-member derives by fractional crystallization from the magmas leftover after the previous UP eruptions. The enclave magma differentiation develops mainly by fractional crystallization associated with multiple mixing with mafic melts changing their composition with time. A time-related picture of the relationships between dome-lavas and relative enclaves is proposed, suggesting a delay between a mafic magma input and the relative dome outpouring. We also infer that the magma viscosity reduction by re-heating allows dome extrusion without explosive activity.     

Revision of the age of magnetization of the Montmartin red beds, Normandy, France

Summary. A new roadcut has enabled us to sample the south-dipping limb of the Montmartin syncline for a palaeomagnetic reevaluation of an earlier result published by Jones, Van der Voo & Bonhommet. In combination with the results previously published in 1979 for the north-dipping beds of the syncline, a conclusively negative fold test is obtained. The resulting magnetization (declination/inclination =206°/-3°, α₉₅= 12°, palaeopole at 38°S, 325°E) is interpreted to be of Late Carboniferous age, not Late Devonian as thought earlier. Simultaneously, we have re-evaluated the age of the rocks, previously thought to be Late Devonian on the basis of Acritarchs, Chitinozoans and spores. It has not been possible to reconfirm these fossils, not even in the same samples as studied originally; in contrast, the regional presence of Early Palaeozoic fossils suggests to us an age similar to that of other red beds in the Arrnorican Massif, which have been dated as Early Ordovician. The geodynamic implications of our finding that the Montmartin rocks are completely remagnetized, however, are of no great consequence for the geodynamics of the Hercynian belt. Pre-folding magnetization obtained from Silurian and Devonian rocks in Spain and Germany argue for the same conclusion as reached erroneously in our earlier study, namely that the Armorican Massif and adjacent parts of Hercynian Europe were adjointed to North America, Great Britain, the Baltic Shield and the Russian Platform since at least Late Devonian time. If a Medio-European ocean existed during the Palaeozoic, it was virtually closed before the mid-Devonian and of insignificant width during Culm deposition in Early Carboniferoirs time.     

X‐ray tomography of tsunami deposits: Towards a new depositional model of tsunami deposits

X‐ray computed microtomography is used to obtain high resolution imagery of a historical tsunami deposit in Andalusia, Spain (1755 Lisbon tsunami). The technique allows characterization of grain‐size distribution, structures, component analysis and sedimentary fabric of fine‐grained unconsolidated tsunami deposits at resolutions down to particle scale. The results are validated by comparing to data obtained using other techniques such as laser diffraction, anisotropy of magnetic susceptibility and X‐ray microfluorescence on the same deposits. Specific technical details such as sampling, scanning and image processing methods, and further improvements are addressed. The use of X‐ray computed microtomography provides new insights into the stratigraphy of the deposits and gives access to significantly more detailed view of key sedimentary features such as mudlines, rip‐up clasts, crude laminations, convolutions, floating outsized clasts and contacts between successive units. This analysis of the 1755 tsunami deposits using X‐ray computed microtomography allows the proposal of new hypotheses for the sedimentary processes forming tsunami deposits. Deposition by settling is limited and the section analysed here is dominated by a high shear stress leading to the development of traction carpets, with laminated mudlines corresponding to the basal frictional region of these carpets. The onset of the tsunami backwash is marked by a micro‐vortex resembling Kelvin–Helmoltz instabilities.     

Numerical simulation and validation of ocean waves measured by an Along-Track Interferometric Synthetic Aperture Radar

A new nonlinear integral transform of ocean wave spectra into Along-Track Interferometric Synthetic Aperture Radar （ATI-SAR） image spectra is described. ATI-SAR phase image spectra are calculated for various sea states and radar configurations based on the nonlinear integral transform. The numerical simulations show that the slant range to velocity ratio （R/V）, significant wave height to ocean wavelength ratio （Hi2）, the baseline （2B） and incident angle （0） affect ATI-SAR imaging. The ATI-SAR imaging theory is validated by means of Two X-band, HH-polarized ATI-SAR phase images of ocean waves and eight C-band, HH-polarized ATI-SAR phase image spectra of ocean waves. It is shown that ATI-SAR phase image spectra are in agreement with those calculated by forward mapping in situ directional wave spectra collected simultaneously with available ATI-SAR observations. ATI-SAR spectral correlation coefficients between observed and simulated are greater than 0.6 and are not sensitive to the degree of nonlinearity. However, the ATI-SARoPhase image spectral turns towards the range direction, even if the real ocean wave direction is 30. It is also shown that the ATI-SAR imaging mechanism is significantly affected by the degree of velocity bunching nonlinearity, especially for high values of R/V and H/2.