A micro-Mössbauer study of chromites included in diamond and other mantle-related rocks

Oxygen fugacity ( $ f_{{{\text{O}}_{ 2} }} $ f O 2 ) is a fundamental but little known intensive variable in mantle processes. It influences the P/T position of a mantle solidus and the composition of mantle-derived melts and fluids and constrains mantle-core equilibria and a number of geophysical properties of the mantle. An important source of information on oxidation states is the ferric–ferrous iron ratio in mantle spinels. Since the magnetite component is low in mantle spinels, normal analytical errors translate into considerable $ f_{{{\text{O}}_{ 2} }} $ f O 2 uncertainties. In this study, we analyzed the Fe³⁺–Fe_tot ratio of chromites present as inclusions in diamond and other mantle-related occurrences by point-source Mössbauer spectroscopy using single-crystal absorbers as well as conventional Mössbauer spectroscopy using powder absorbers. The studied spinels have been previously analyzed by single-crystal X-ray diffraction and electron microprobe. The ferric–ferrous ratios found are normally similar to the different techniques apart from some samples where a large number of grains have been used for the analyses (powder absorbers). The general agreement between the different techniques allows us to conclude that the studied chromites are stoichiometric. However, conventional Mössbauer spectroscopy on powder absorbers should be conducted with great care, since the method requires a relatively large amount of sample material. Spinel frequently occurs as small grains, and the large number of crystals required may possess different degrees of oxidation/alteration and, consequently, different ferric–ferrous ratio leading to possible errors in the interpretation of the results.     

Slope stabilization in difficult conditions: the case study of a debris slide in NW Italian Alps

A case study of a debris slide (estimated volume of about 35,000 m³) is described in this paper. This slide occurred in April 2009 in the North Western Italian Alps (Aosta valley) and damaged the SR25 road along the Valgrisenche valley. Ground investigations started with severe safety and logistic issues being posed. Given the need to open as soon as possible the road, the design of the landslide stabilization works was carried out using a “design as you go” approach. The stabilization measures were conceived to be flexible in order to allow for changes and integration during construction, in line with the progressive refinement of the geological–geotechnical slope model being developed. Back analysis by means of the limit equilibrium method (LEM) and the finite element method (FEM) was used. Groundwater level rise following heavy rainfall and spring snow melting was found to be the main cause of the debris slide. The stabilization works were designed by using both the LEM and FEM methods. The stability conditions of the engineered slope were assessed based on the available performance monitoring data.     

Application of Compositional Techniques in the Field of Crystal Chemistry: A Case Study of Luzonite, a Sn-Bearing Mineral

Out-of-equilibrium crystallization often produces complex compositional variability in minerals, generating zoning and other mixing phenomena. The appropriate microchemical characterization of the resulting out-of-equilibrium patterns is of critical importance in understanding the overall physical and chemical properties of the host crystalline phases. In this framework, the modeling of compositional changes assumes a fundamental role. However, when compositional data are used, their management with standard exploratory, statistical, graphical, and numerical tools may give misleading results attributable to the phenomenon of induced correlations. To avoid these problems, methods able to extract compositional data from their constrained space (the simplex) in order to apply standard statistics, have to be adopted. As an alternative, the use of tools having properties able to work in the simplex geometry has to be considered. A luzonite single crystal (ideal composition, Cu₃AsS₄) exhibiting concentric and sector zoning was studied using electron probe microanalysis in order to understand the mechanisms which give rise to chemical variability and conditions in the developing environment. Compositional variations were determined by collecting data along three different transects. The major and minor elements (Cu, As, S, Fe, Sb, Sn) were analyzed with the aim of characterizing their patterns of association in the crystal and, hence, crystal evolution. The whole covariance structure as well as the chemical relationships between the successive zones was investigated by means of compositional methods, considering both data transformation and the stay in the simplex approach. Results indicate that the crystal grew under quiescent conditions, where chemical control was primarily exercised by the mineral’s surface and only minor effects were due to changes in the composition of the surrounding fluid. Consequently, an oscillatory uptake of chemical components occurred in which a competition between famatinite-like (Cu₃SbS₄) and kuramite-like (Cu₃SnS₄) domains characterized the As-poor zones.     

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 »     

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.     

Copula-based mixed models for bivariate rainfall data: an empirical study in regression perspective

A comprehensive parametric approach to study the probability distribution of rainfall data at scales of hydrologic interest (e.g. from few minutes up to daily) requires the use of mixed distributions with a discrete part accounting for the occurrence of rain and a continuous one for the rainfall amount. In particular, when a bivariate vector (X, Y) is considered (e.g. simultaneous observations from two rainfall stations or from two instruments such as radar and rain gauge), it is necessary to resort to a bivariate mixed model. A quite flexible mixed distribution can be defined by using a 2-copula and four marginals, obtaining a bivariate copula-based mixed model. Such a distribution is able to correctly describe the intermittent nature of rainfall and the dependence structure of the variables. Furthermore, without loss of generality and with gain of parsimony this model can be simplified by some transformations of the marginals. The main goals of this work are: (1) to empirically explore the behaviour of the parameters of marginal transformations as a function of time scale and inter-gauge distance, by analysing data from a network of rain gauges; (2) to compare the properties of the regression curves associated to the copula-based mixed model with those derived from the model simplified by transformations of the marginals. The results from the investigation of transformations’ parameters are in agreement with the expected theoretical dependence on inter-gauge distance, and show dependence on time scale. The analysis on the regression curves points out that: (1) a copula-based mixed model involves regression curves quite close to some non-parametric models; (2) the performance of the parametric regression decreases in the same cases in which non-parametric regression shows some instability; (3) the copula-based mixed model and its simplified version show similar behaviour in term of regression for mid-low values of rainfall. An erratum to this article can be found at     

Thermal decay of carbonate dimension stones: fabric,physical and mechanical changes

This paper deals with the effects of thermal stresses on selected carbonate rocks used as dimension stones. They are Mesozoic calcareous and dolomitic rocks cropping out in Apulia (southern Italy) that, for their physico-mechanical and aesthetic properties, have always been finding a large application both as ornamental stones and as simple construction materials; their use is attested not only in Italy, in works of archaeological, historical and artistic interest too. The cause–effect relationships of thermal degradation were studied by means of an artificial accelerated ageing test, in order to provide a perspective about the decay of carbonate stones due to diurnal and seasonal temperature fluctuations, as well as thermal shocks during events of fire development. The stone samples were subjected to thermal cycles in a muffle furnace, ranging from 100 to 700 °C; after each cycle, several non-destructive and semi-destructive tests were carried out: mass and volume measurements, mercury intrusion porosimetry, sclerometer tests, ultrasonic tests, thin-section observations and determination of chromatic alterations through image analysis and Munsell charts method. In this way, the qualitative and quantitative modifications induced in fabric, physical and mechanical properties were discussed. The results highlight the fundamental role of depositional and diagenetic fabric that, together with mineralogical composition, represents the most significant discriminating factor in the response of the stone to thermal stresses.     

Impacts of extreme weather on wheat and maize in France: evaluating regional crop simulations against observed data

Extreme weather conditions can strongly affect agricultural production, with negative impacts that can at times be detected at regional scales. In France, crop yields were greatly influenced by drought and heat stress in 2003 and by extremely wet conditions in 2007. Reported regional maize and wheat yields where historically low in 2003; in 2007 wheat yields were lower and maize yields higher than long-term averages. An analysis with a spatial version (10?×?10?km) of the EPIC crop model was tested with regards to regional crop yield anomalies of wheat and maize resulting from extreme weather events in France in 2003 and 2007, by comparing simulated results against reported regional crops statistics, as well as using remotely sensed soil moisture data. Causal relations between soil moisture and crop yields were specifically analyzed. Remotely sensed (AMSR-E) JJA soil moisture correlated significantly with reported regional crop yield for 2002–2007. The spatial correlation between JJA soil moisture and wheat yield anomalies was positive in dry 2003 and negative in wet 2007. Biweekly soil moisture data correlated positively with wheat yield anomalies from the first half of June until the second half of July in 2003. In 2007, the relation was negative the first half of June until the second half of August. EPIC reproduced observed soil dynamics well, and it reproduced the negative wheat and maize yield anomalies of the 2003 heat wave and drought, as well as the positive maize yield anomalies in wet 2007. However, it did not reproduce the negative wheat yield anomalies due to excessive rains and wetness in 2007. Results indicated that EPIC, in line with other crop models widely used at regional level in climate change studies, is capable of capturing the negative impacts of droughts on crop yields, while it fails to reproduce negative impacts of heavy rain and excessively wet conditions on wheat yield, due to poor representations of critical factors affecting plant growth and management. Given that extreme weather events are expected to increase in frequency and perhaps severity in coming decades, improved model representation of crop damage due to extreme events is warranted in order to better quantify future climate change impacts and inform appropriate adaptation responses.     

Calcio-carbonatite melts and metasomatism in the mantle beneath Mt. Vulture (Southern Italy)

At Mt. Vulture volcano (Basilicata, Italy) calcite globules (5–150 μm) are hosted by silicate glass pools or veins cross-cutting amphibole-bearing, or more common spinel-bearing mantle xenoliths and xenocrysts. The carbonate globules are rounded or elongated and are composed of a mosaic of 2–20 μm crystals, with varying optical orientation. These features are consistent with formation from a quenched calciocarbonatite melt. Where in contact with carbonate amphibole has reacted to form fassaitic pyroxene. Some of these globules contain liquid/gaseous CO₂ bubbles and sulphide inclusions, and are pierced by quench microphenocrysts of silicate phases. The carbonate composition varies from calcite to Mg-calcite (3.8–5.0 wt.% MgO) both within the carbonate globules and from globule to globule. Trace element contents of the carbonate, determined by LAICPMS, are similar to those of carbonatites worldwide including ΣREE up to 123 ppm. The Sr–Nd isotope ratios of the xenolith carbonate are similar to the extrusive carbonatite and silicate rocks of Mt. Vulture testifying to derivation from the same mantle source. Formation of immiscibile silicate–carbonatite liquids within mantle xenoliths occurred via disequilibrium immiscibility during their exhumation.