ESEEM of industrial quartz powders: insights into crystal chemistry of Al defects

A set of raw industrial materials, that is, pure quartz and quartz-rich mixtures, were investigated through electron paramagnetic resonance and electron spin echo-envelope modulation spectroscopies, with the aim of evaluating the effective role played by defect centres and of assessing whether they can be used to monitor changes in the physical properties of quartz powders with reference to their health effects. The obtained results point to two interactions of the Al defect centres with H⁺, hosted in sites within the channels parallel and perpendicular to the c axis of quartz, respectively. These two Al/H⁺ (h_Al) centres exhibit a weak chemical bond, and their relative amounts appear to be modified/controlled by the thermo-mechanical processes underwent by powders. Indeed, a mechanically promoted inter-conversion between the two kinds of site is suggested. As a consequence, the h_Al centres are effective in monitoring even modest activations of powders, through thermal or mechanical processes, and they are also supposed to play a specific, relevant role in quartz reactivity during the considered industrial processes.     

Magnetic behavior of trioctahedral micas with different octahedral Fe ordering

This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition ^IV(Si_2.76Al_1.24) ^VI(Al_0.64Mg_0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn_0.03Ti_0.15) (K_0.96Na_0.05) O_10.67 (OH)_1.31 Cl_0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition ^IV(Si_3.14Al_0.86)^VI(Al_0.75Mg_0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn_0.01Ti_0.01Li_1.09) (K_0.99Na_0.01) O_10.00 (OH)_0.65F_1.35]. Samples differ for Fe ordering in octahedral sites, Fe²⁺/(Fe²⁺?+?Fe³⁺) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.     

Benthic foraminifera distribution in a tourist lagoon in Rio de Janeiro, Brazil: a response to anthropogenic impacts

Rodrigo de Freitas Lagoon, located in the Rio de Janeiro City, receives several types of polluted discharges. The knowledge of the sediment microfauna correlated with heavy metal and organic matter concentrations could supply important data about the conditions of the lagoon. The benthic foraminiferal assemblage presented larger diversity and more abundant samples in the lagoon entrance than in the inner area. The Ammonia tepida - Elphidiumexcavatum foraminiferal assemblage is characterized by dwarf, corroded and weak organisms. Agglutinated species were found only near the entrance. Low abundance values and sterility of five samples in the inner area (north/northeast) can be caused by high levels of heavy metals and organic matter. A. tepida shows negative correlation with increasing heavy metals values. PAHs and coprostanol high indexes, and the absence or low presence of microfauna in samples around the lagoon margin confirm illegal flows from gas stations and domestic sewage.     

Critical appraisal on the identification of Reference Conditions for the evaluation of ecological quality status along the Emilia-Romagna coast (Italy) using M-AMBI

According to the European Water Framework Directive, the ecological status (ES) of a water body is determined by comparing observation data with undisturbed Reference Conditions (RCs). Defining RCs is crucial when evaluating the ES of a water body as it strongly affects the final outcome of any index application. Identifying RCs by observing real sites is not feasible in many marine environments, such as the Emilia-Romagna coast (Italy, N-Adriatic Sea). We used a statistical approach on a large dataset to derive RCs for the application of the benthic index M-AMBI in this area. We then applied M-AMBI to samples collected along a gradient of presumed environmental disturbance. The results put 14.8% of the Emilia-Romagna samples in “High” ES, 60.2% in “Good”, 23.0% in “Moderate” and 2.0% in “Poor”, showing a spatial gradient of improving quality. These results are in agreement with the extensive ecological knowledge available for this area.     

High-temperature emplacement of the Cerro Galán and Toconquis Group ignimbrites (Puna plateau,NW Argentina) determined by TRM analyses

Estimates of pyroclastic flow emplacement temperatures in the Cerro Galán ignimbrite and Toconquis Group ignimbrites were determined using thermal remanent magnetization of lithic clasts embedded within the deposits. These ignimbrites belong to the Cerro Galán volcanic system, one of the largest calderas in the world, in the Puna plateau, NW Argentina. Temperature estimates for the 2.08-Ma Cerro Galán ignimbrite are retrieved from 40 sites in 14 localities (176 measured clasts), distributed at different distances from the caldera and different stratigraphic heights. Additionally, temperature estimates were obtained from 27 sample sites (125 measured clasts) from seven ignimbrite units forming the older Toconquis Group (5.60–4.51 Ma), mainly outcropping along a type section at Rio Las Pitas, Vega Real Grande. The paleomagnetic data obtained by progressive thermal demagnetization show that the clasts of the Cerro Galán ignimbrite have one single magnetic component, oriented close to the expected geomagnetic field at the time of emplacement. Results show therefore that most of the clasts acquired a new magnetization oriented parallel to the magnetic field at the moment of the ignimbrite deposition, suggesting that the clasts were heated up to or above the highest blocking temperature (T _b) of the magnetic minerals (T _b = 580°C for magnetite; T _b = 600–630°C for hematite). We obtained similar emplacement temperature estimations for six out of the seven volcanic units belonging to the Toconquis Group, with the exception of one unit (Lower Merihuaca), where we found two distinct magnetic components. The estimation of emplacement temperatures in this latter case is constrained at 580–610°C, which are lower than the other ignimbrites. These estimations are also in agreement with the lowest pre-eruptive magma temperatures calculated for the same unit (i.e., 790°C; hornblende–plagioclase thermometer; Folkes et al. 2011b). We conclude that the Cerro Galán ignimbrite and Toconquis Group ignimbrites were emplaced at temperatures equal to or higher than 620°C, except for Lower Merihuaca unit emplaced at lower temperatures. The homogeneity of high temperatures from proximal to distal facies in the Cerro Galán ignimbrite provides constraints for the emplacement model, marked by a relatively low eruption column, low levels of turbulence, air entrainment, surface–water interaction, and a high level of topographic confinement, all ensuring minimal heat loss.     

Fossil brines preserved in the St-Lawrence Lowlands, Québec, Canada as revealed by their chemistry and noble gas isotopes

Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Bécancour, Québec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na-Ca-Cl type, possibly derived from halite dissolution. ⁸⁷Sr/⁸⁶Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2-3% contribution of mantle ³He and large amounts of nucleogenic ²¹Ne^∗ and ³⁸Ar^∗ and radiogenic ⁴He and ⁴⁰Ar^∗. ⁴He/⁴⁰Ar^∗ and ²¹Ne^∗/⁴⁰Ar^∗ ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of ⁴⁰Ar^∗ in brines constrain the residence time of Bécancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian-Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian-Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic ⁴⁰Ar^∗ into the brines. The last thermal event that could have facilitated the liberation of ⁴⁰Ar^∗ into fluids and contributed to mantle ³He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Bécancour brines.     

Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu₃SnS₄, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu₃SnS₄ crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)₂Cu(II)SnS₄ and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.     

Nouvelles données sur le Messinien de Méditerranée occidentale : les gisements à Aphanius crassicaudus (Agassiz poissons téléostéens,cyprinodontiformes) des Marches (Italie)

Résumén

La découverte, dans le Nord des Marches (Italie), de nouveaux gisements de Poissons Cyprinodontidae appartenant à l’espèce Aphanius crassicaudus (AGASSIZ), conduit à réexaminer, à la lumière des données lithostratigraphiques, la signification géodynamique des ichthyofaunes messiniennes de ce secteur de l’Apennin. Après avoir précisé la position stratigraphique et la répartition paléogéographique des gisements étudiés, les auteurs montrent que le développement des faunes à Aphanius crassicaudus (AGASSIZ) dans les eaux saumâtres du domaine continental n’implique pas la disparition corrélative du milieu marin. En effet, certains genres marins sont parfois présents à côté de cette espèce, comme c’est le cas dans le gisement de Pésaro. Les auteurs contestent en outre l’interprétation selon laquelle le fait qu’aucune ichthyofaune marine ne soit connue dans le Messinien supérieur d’Italie puisse suffire à conclure que la Méditerranée était asséchée pendant le dépôt de la « Formation à colombacci »     

The Ligurian Helminthoid flysch units of the Emilian Apennines: stratigraphic and petrographic features,paleogeographic restoration and structural evolution

Abstract

This work deals with the Cretaceous-Tertiary Helminthoid flysch successions of the Emilian Apennines and related basal complexes (Mt. Caio, Val Baganza, Solignano, Mt. Venere-Monghidoro and Mt. Cassio Units): it is based on an integrated approach which included stratigraphic, petrographic and structural observations. Detailed stratigraphic sections measured in the various successions evidenced the specific features of the different flysch formations. The main framework composition analysis of the arenites pointed out a partly ‘oceanic’ alimentation for the Mt. Caio Flysch Fm; the Mt. Venere-Monghidoro, and Mt. Cassio Flysch Fms have been alimented exclusively by a terrigenous detritus mainly derived from continental basement source areas. The heavy mineral assemblage of the Mt. Caio Flysch Fm is characterized by picotite, that of the Mt. Venere-Monghidoro, Solignano and Mt. Cassio Flysch Fms commonly contains straurolite, garnet and chloritoid, generally considered to be typical products of the Adriatic continental margin. The calcareous nannofossils biostratigraphy indicated that the flysch sedimentation started during the Late Campanian and ended between the Paleocene (Mt. Cassio Flysch Fm and Mt. Venere-Monghidoro Fms) and the Middle Eocene (Mt. Caio Flysch Fm). We propose a schematic paleogeographic restoration for the External Ligurian Domain which implies a more internal position for the Mt. Caio succession and a more external one for the Mt. Venere-Monghidoro and Mt. Cassio successions. The Helminthoid flyschs sedimented after and during deformation and subduction phases in perched and fore-arc basins partly overlying the marginal part of the Adriatic plate. The External Ligurian nappes’ stacking consists, in the study area, from the bottom, of the following units: Caio Unit, Val Baganza Ophiolitic Unit, Monghidoro Unit, Cassio Unit. This pile of thrust-nappes, sealed by the Epiligurian succession, has been already realized before Late Eocene. In our opinion it was generated by a frontal west-verging frontal accretion process (offscraping), which let the flysch successions remain, in this phase, quite undeformed. This westverging thrusting phase, starting from the Middle-Late Eocene, has been followed by an important folding event which generated striking hectometric and kilometric ‘Apenninic’ reverse folds, sometimes associated with NE-verging thrust surfaces. The Oligocene and post-Oligocene evolution is characterized by a block-translation of the Ligurian staking over the Subligurian, Tuscan and Umbrian Domains, associated with a new generation of minor thrusts and thrust related Apenninic folds. © 2000 Éditions scientifiques et médicales Elsevier SAS