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     

Reionization and the Cosmic Dawn with the Square Kilometre Array

The Square Kilometre Array (SKA) will have a low frequency component (SKA-low) which has as one of its main science goals the study of the redshifted 21 cm line from the earliest phases of star and galaxy formation in the Universe. This 21 cm signal provides a new and unique window both on the time of the formation of the first stars and accreting black holes and the subsequent period of substantial ionization of the intergalactic medium. The signal will teach us fundamental new things about the earliest phases of structure formation, cosmology and even has the potential to lead to the discovery of new physical phenomena. Here we present a white paper with an overview of the science questions that SKA-low can address, how we plan to tackle these questions and what this implies for the basic design of the telescope.     

Comparing efficacy of different taxonomic resolutions and surrogates in detecting changes in soft bottom assemblages due to coastal defence structures

Sandy shores on the West coast of the North Adriatic Sea are extensively protected by different types of defence structures to prevent coastal erosion. Coastal defence schemes modify the hydrodynamic regime, the sediment structure and composition thus affecting the benthic assemblages. This study examines the effectiveness in detecting changes in soft bottom assemblages caused by coastal defence structures by using different levels of taxonomic resolution, polychaetes and/or bivalves as surrogates and different data transformations. A synoptic analyses of three datasets of subtidal benthic macrofauna used in studies aimed at assessing the impact of breakwaters along the North Adriatic coast has been done. Analyses of similarities and correlations between distance matrices were done using matrices with different levels of taxonomic resolution, and with polychaetes or bivalves data alone. Lentidium mediterraneum was the most abundant species in all datasets. Its abundance was not consistently related to the presence of defence structures. Moreover, distribution patterns of L. mediterraneum were masking the structure of the whole macrofaunal assemblages. Removal of L. mediterraneum from the datasets allowed the detection of changes in benthic assemblages due to coastal defences. Analyses on different levels of taxonomic resolution showed that the level of family maintained sufficient information to detect the impacts of coastal defence structures on benthic assemblages. Moreover, the outcomes depended on the transformation used. Patterns of distribution of bivalves, used as surrogates, showed low correlations with the patterns of the total macrofaunal species assemblages. Patterns of polychaetes, if identified to the species or genus level showed higher correlations with the whole dataset. However, the identification of polychaetes to species and genus level is as costly as the identification of all macrobenthic taxa at family level.This study provided additional evidences that taxonomic sufficiency is a useful tool in environmental monitoring, also in investigations on the impacts of coastal defence structures on subtidal macrofauna. The use of coarser taxonomic level, being time-efficient, would allow improving sampling designs of monitoring programs by increasing replication in space and time and by allowing long term monitoring studies.     

Controls on event runoff coefficients in the eastern Italian Alps

Analyses of event runoff coefficients provide essential insight on catchment response, particularly if a range of catchments and a range of events are compared by a single indicator. In this study we examine the effect of climate, geology, land use, flood types and initial soil moisture conditions on the distribution functions of the event runoff coefficients for a set of 14 mountainous catchments located in the eastern Italian Alps, ranging in size from 7.3 to 608.4 km². Runoff coefficients were computed from hourly precipitation, runoff data and estimates of snowmelt. A total of 535 events were analysed over the period 1989–2004. We classified each basin using a “permeability index” which was inferred from a geologic map and ranged from “low” to “high permeability”. A continuous soil moisture accounting model was applied to each catchment to classify ‘wet’ and ‘dry’ initial soil moisture conditions. The results indicate that the spatial distribution of runoff coefficients is highly correlated with mean annual precipitation, with the mean runoff coefficient increasing with mean annual precipitation. Geology, through the ‘permeability index’, is another important control on runoff coefficients for catchments with mean annual precipitation less than 1200 mm. Land use, as indexed by the SCS curve number, influences runoff coefficient distribution to a lesser degree. An analysis of the runoff coefficients by flood type indicates that runoff coefficients increase with event snowmelt. Results show that there exists an intermediate region of subsurface water storage capacity, as indexed by a flow–duration curve-based index, which maximises the impact of initial wetness conditions on the runoff coefficient. This means that the difference between runoff coefficients characterised by wet and dry initial conditions is negligible both for basins with very large storage capacity and for basins with small storage capacity. For basins with intermediate storage capacities, the impact of the initial wetness conditions may be relatively large.     

Physical processes contributing to the water mass transformation of the Indonesian Throughflow

The properties of the waters that move from the Pacific to the Indian Ocean via passages in the Indonesian archipelago are observed to vary with along-flow-path distance. We study an ocean model of the Indonesian Seas with reference to the observed water property distributions and diagnose the mechanisms and magnitude of the water mass transformations using a thermodynamical methodology. This model includes a key parameterization of mixing due to baroclinic tidal dissipation and simulates realistic water property distributions in all of the seas within the archipelago. A combination of air–sea forcing and mixing is found to significantly change the character of the Indonesian Throughflow (ITF). Around 6 Sv (approximately 1/3 the model net ITF transport) of the flow leaves the Indonesian Seas with reduced density. Mixing transforms both the intermediate depth waters (transforming 4.3 Sv to lighter density) and the surface waters (made denser despite the buoyancy input by air–sea exchange, net transformation?=?2 Sv). The intermediate transformation to lighter waters suggests that the Indonesian transformation contributes significantly to the upwelling of cold water in the global conveyor belt. The mixing induced by the wind is not driving the transformation. In contrast, the baroclinic tides have a major role in this transformation. In particular, they are the only source of energy acting on the thermocline and are responsible for creating the homostad thermocline water, a characteristic of the Indonesian outflow water. Furthermore, they cool the sea surface temperature by between 0.6 and 1.5°C, and thus allow the ocean to absorb more heat from the atmosphere. The additional heat imprints its characteristics into the thermocline. The Indonesian Seas cannot only be seen as a region of water mass transformation (in the sense of only transforming water masses in its interior) but also as a region of water mass formation (as it modifies the heat flux and induced more buoyancy flux). This analysis is complemented with a series of companion numerical experiments using different representations of the mixing and advection schemes. All the different schemes diagnose a lack of significant lateral mixing in the transformation.     

Late Quaternary deformation on the island on Pantelleria: New constraints for the recent tectonic evolution of the Sicily Channel Rift (southern Italy)

Structural observations carried out on the volcanic Island of Pantelleria show that the tectonic setting is dominated by NNE trending normal faults and by NW-striking right-lateral strike-slip faults with normal component of motion controlled by a ≈N 100°E oriented extension. This mode of deformation also controls the development of the eruptive fissures, dykes and eruptive centres along NNE–SSW belts that may thus represent the surface response to crustal cracking with associated magma intrusions. Magmatic intrusions are also responsible for the impressive vertical deformations that affect during the Late Quaternary the south-eastern segment of the island and producing a large dome within the Pantelleria caldera complex. The results of the structural analysis carried out on the Island of Pantelleria also improves the general knowledge on the Late Quaternary tectonics of the entire Sicily Channel. ESE–WNW directed extension, responsible for both the tectonic and volcano-tectonic features of the Pantelleria Island, also characterizes, at a greater scale, the entire channel as shown by available geodetic and seismological data. This mode of extension reactivates the older NW–SE trending fault segments bounding the tectonic troughs of the Channel as right-lateral strike-slip faults and produces new NNE trending pure extensional features (normal faulting and cracking) that preferentially develop at the tip of the major strike-slip fault zones. We thus relate the Late Quaternary volcanism of the Pelagian Block magmatism to dilatational strain on the NNE-striking extensional features that develop on the pre-existing stretched area and propagate throughout the entire continental crust linking the already up-welled mantle with the surface.     

Potentially modified hydropower production under climate change in the Italian Alps

We present an assessment of the potential impacts of climate change on hydropower production within a paradigmatic, very highly exploited cryospheric area of upper Valtellina valley in the Italian Alps. Based on dependable and unique hydrological measures from our high‐altitude hydrometric network Idrostelvio during 2006–2015, we set up the Poly‐Hydro model to mimic the cryospheric processes driving hydrological flow formation in this high‐altitude area. We then set up an optimization tool, which we call Poly‐Power, to maximize the revenue of the plant manager under given hydrological regimes, namely, by proper operation of the hydroelectric production scheme (reservoirs, pipelines, and power plants) of the area. We then pursue hydrological projections until 2100, feeding Poly‐Hydro with the downscaled outputs of three general circulation models from the Intergovernmental Panel on Climate Change Fifth Assessment Report, under the scenarios Representative Concentration Pathway (RCP) 2.6, RCP 4.5, and RCP 8.5. We assess hydrological flows in two reference decades, that is, at half century (2040–2049), and end of century (2090–2099). We then feed the so obtained hydrological scenarios as inputs to Poly‐Power, and we project future production of hydroelectric power, with and without reoperation of the system. The average annual stream flows for hydropower production decreases along the century under our scenarios (?21 to +7%, on average ? 5% at half century; ?17 to ?2%, average ? 8%, end of century), with ice cover melting unable to offset such decrease. Reduction in snowfall and increase in liquid rainfall are the main factors affecting the modified hydrological regime. Energy production (and revenues) at half century may increase under our scenarios (?9 to +15%, +3% on average). At the end of century in spite of a projected increase on average (?7 to +6%, +1% on average), under the warmest scenario RCP 8.5 decrease of energy production is consistently projected (?4% on average). Our results provide an array of potential scenarios of modified hydropower production under future climate change and may be used for brain storming of adaptation strategies.     

Numerical modelling of stream–aquifer interaction: Quantifying the impact of transient streambed permeability and aquifer heterogeneity

Stream–aquifer interaction plays a vital role in the water cycle, and a proper study of this interaction is needed for understanding groundwater recharge, contaminants migration, and for managing surface water and groundwater resources. A model‐based investigation of a field experiment in a riparian zone of the Schwarzbach river, a tributary of the Rhine River in Germany, was conducted to understand stream–aquifer interaction under alternative gaining and losing streamflow conditions. An equivalent streambed permeability, estimated by inverting aquifer responses to flood waves, shows that streambed permeability increased during infiltration of stream water to aquifer and decreased during exfiltration. Aquifer permeability realizations generated by multiple‐point geostatistics exhibit a high degree of heterogeneity and anisotropy. A coupled surface water groundwater flow model was developed incorporating the time‐varying streambed permeability and heterogeneous aquifer permeability realizations. The model was able to reproduce varying pressure heads at two observation wells near the stream over a period of 55 days. A Monte Carlo analysis was also carried out to simulate groundwater flow, its age distribution, and the release of a hypothetical wastewater plume into the aquifer from the stream. Results of this uncertainty analysis suggest (a) stream–aquifer exchange flux during the infiltration periods was constrained by aquifer permeability; (b) during exfiltration, this flux was constrained by the reduced streambed permeability; (c) the effect of temporally variable streambed permeability and aquifer heterogeneity were found important to improve the accurate capture of the uncertainty; and (d) probabilistic infiltration paths in the aquifer reveal that such pathways and the associated prediction of the extent of the contaminant plume are highly dependent on aquifer heterogeneity.