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.     

Modeling water resources of a highly irrigated alluvial plain (Italy): calibrating soil and groundwater models

Modern and effective water management in large alluvial plains that have intensive agricultural activity requires the integrated modeling of soil and groundwater. The models should be complex enough to properly simulate several, often non-linear, processes, but simple enough to be effectively calibrated with the available data. An operative, practical approach to calibration is proposed, based on three main aspects. First, the coupling of two models built on well-validated algorithms, to simulate (1) the irrigation system and the soil water balance in the unsaturated zone and (2) the groundwater flow. Second, the solution of the inverse problem of groundwater hydrology with the comparison model method to calibrate the model. Third, the use of appropriate criteria and cross-checks (comparison of the calibration results and of the model outputs with hydraulic and hydrogeological data) to choose the final parameter sets that warrant the physical coherence of the model. The approach has been tested by application to a large and intensively irrigated alluvial basin in northern Italy.     

Nitrate source and fate at the catchment scale of the Vibrata River and aquifer (central Italy): an analysis by integrating component approaches and nitrogen isotopes

The aim of this study is to apply an integrated approach to determine nitrate sources and fate in the alluvial aquifer of the River Vibrata (Abruzzi, central Italy) by coupling the Isotope and the Component approaches. Collected data include concentration and nitrogen isotope composition of groundwater samples from the alluvial aquifer and nitrogen loads arising from agricultural and non-agricultural sources. The adopted methodology identified synthetic fertilizers as main sources of nitrate in the Vibrata alluvial aquifer. At the catchment scale, two different zones have been identified: the Upper Valley, where infiltration to groundwater is dominant and nitrogen easily migrates into the aquifer; in this area, nitrate content in groundwater is stable and normally higher than EU requirements. Moreover, streamwaters are fed by groundwater with a nitrate content likely lowered by denitrification processes occurring in the hyporheic zone. In the Lower Valley, runoff processes dominate and the nitrate content in surface waters is higher. Nevertheless, groundwater is locally affected by denitrification that breaks down the nitrate content, which often reaches values consistent with law limits.     

Modelling hydrostratigraphy and groundwater flow of a fractured and karst aquifer in a Mediterranean basin (Salento peninsula, southeastern Italy)

The control exerted by the hydrostratigraphic structure on aquifer recharge, groundwater flow and discharge along the coastal areas of a Mediterranean basin (Salento peninsula, about 5,000?km² wide, southern Italy) is assessed through the development and application of a groundwater flow model based on the reconstruction of the hydrostratigraphic architecture at the regional scale. The hydrostratigraphic model, obtained by processing surface and subsurface data, is applied to map the top of the main aquifer, which is hosted in the deep hydrostratigraphic unit corresponding to Cretaceous and Oligocene limestones with complex geometrical relationships with the sea. It is also used to estimate the aquifer recharge, which occurs by percolation through overlying younger sediments with low permeability. These data are completed with information about the soil use to estimate water abstraction for irrigation and with literature data to estimate the water abstraction for drinking and industrial purposes. The above-sketched conceptual model is the basis for a finite difference groundwater 2D pseudo-stationary flow model, which assumes the following fundamental approximations: the fractured and karst limestone hydrostratigraphic unit can be approximated, at the model scale, as a continuous medium for which the discrete Darcy??s law is valid; the transition zone between salt and fresh water is so small with respect to the grid spacing that the Ghyben?CHerzberg??s approximation for a sharp interface can be applied. Along the coastline different boundary conditions are assigned if the top of the limestone hydrostratigraphic unit lies either above the sea level (the aquifer has a free surface and fresh water is drained), or below the sea level (the aquifer is under pressure and the contact with sea occurs off-shore). The groundwater flow model correctly predicts the areas where the aquifer is fully saturated with salt water.     

PCBs in Central Vietnam coastal lagoons: levels and trends in dynamic environments

PCBs were analysed in surficial sediments and selected sediment cores collected between 2002 and 2008 in Central Vietnam coastal lagoons. The aim was to determine contamination levels and trends, and to evaluate the effects of anthropogenic pressures and natural events. Samples were mostly fine-grained with low total PCB concentrations (0.367-44.7 μg kg⁻¹). Atmospheric transport and post depositional processes modify to some degree the fingerprint of PCB inputs to the environment favouring the predominance of 3, 4 and 5 chlorinated congeners. The similarity of congener distributions in contemporary surficial samples also suggests the presence of a unique source over the entire study area, probably connected to mobilisation and long range transports from land-based stocks. The removal of consistent sediment layers is hypothesised based on repeated samplings of the same area. Natural meteorological events (such as typhoons) are suspected to be responsible for these sediment losses.     

Ostreopsis cf. ovata bloom in the northern Adriatic Sea during summer 2009: ecology, molecular characterization and toxin profile

Intense blooms of the benthic dinoflagellate Ostreopsis cf. ovata have occurred in the northern Adriatic Sea since 2006. These blooms are associated with noxious effects on human health and with the mortality of benthic organisms because of the production of palytoxin-like compounds. The O. cf. ovata bloom and its relationships with nutrient concentrations at two stations on the Conero Riviera (northern Adriatic Sea) were investigated in the summer of 2009. O. cf. ovata developed from August to November, with the highest abundances in September (1.3 × 10⁶ cells g⁻¹ fw corresponding to 63.8 × 10³ cells cm⁻²). The presence of the single O. cf. ovata genotype was confirmed by a PCR assay. Bloom developed when the seawater temperature was decreasing. Nutrient concentrations did not seem to affect bloom dynamics. Toxin analysis performed by high resolution liquid chromatography-mass spectrometry revealed a high total toxin content (up to 75 pg cell⁻¹), including putative palytoxin and all the ovatoxins known so far.     

Performance of the Italian strong motion network during the 2009, L��Aquila seismic sequence (central Italy)

On April 6, 2009, the town of L’Aquila in the Abruzzo region (central Italy) was struck by a seismic event at 01:32 (UTC), of magnitude M_W = 6.3. The mainshock was followed by a long period of intense seismic activity and within seven days after the mainshock there were seven events of magnitude M_W ≥ 5 that occurred from April 6 to April 13. This long seismic sequence was characterized by a complex rupture mechanism that involved two major normal faults of the central Apennines: the Paganica and the Gorzano faults. The strong-motions of the mainshock were recorded by 64 stations of the Italian Strong-motion Network (RAN) operated by the National Civil Protection Department (DPC). Six stations of a local strong-motion array were working in NW L’Aquila suburb area. One of them, located at about 6 km from the Paganica fault surface tip-line, set up in trigger mode, recorded continuously for more than 20 min the mainshock and the aftershocks. Besides the mainshock, the RAN stations recorded in total 78 foreshocks and aftershocks of M_L ≥ 3.5, during the period from January to December 2009. The corresponding waveforms provide the most extensive digital strong ground motion data set ever recorded in Italy. Moreover, the 48 three-component observations of events of magnitude M_W ≥ 5, recorded at a distance less than 15 km from each of the major involved faults, provide a significant increasing of near-field records available for the Italian territory. Six days after the mainshock, the strong-motion dataset, referred to preliminary locations of the events with M_L ≥ 4.0, was made available on the DPC web site () and at the same time it was delivered to the ITACA database (). This dataset has been used by many authors in scientific papers and by engineers, geophysicists and geologists for professional technical works. In this paper, the present-day available strong-motion signals from the L’Aquila sequence and the performance of the Italian strong-motion network in terms of the number and quality of recorded data, the geometry and data transmission system are described. In addition the role of the temporary network that represents an extension of the permanent Italian strong-motion network, supporting the emergency response by civil protection authorities and improving the network coverage has been evaluated.     

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.