Natural Cr(VI) contamination of groundwater in the Cecina coastal area and its inner sectors (Tuscany,Italy)

A detailed hydrogeochemical study of groundwater in the Cecina coastal plain (Livorno province, Italy) and its inner sectors was undertaken in 2008, as chemical analyses carried out on groundwater since 2006 have revealed Cr(VI) concentrations of up to 49 μg/L (well above the permissible limit of 5 μg/L). Ophiolite outcrops are present throughout the study area, and their fragments likely represent a significant portion of the existing multilayered aquifer skeleton. Waters delivered by the serpentinite outcrops have a typically Mg–HCO₃ composition, whereas those of the coastal plain are prevailingly of the Ca/Mg–HCO₃ type with significant Mg contents. Significant NO₃ contamination characterises the studied coastal plain, and an interesting negative correlation exists between Cr(VI) and both NO₃ and SO₄ deriving from the widespread use of (NH₄)₂SO₄ as a farm fertilizer. Chromium speciation calculations carried out using the EQ3NR code reveal that the prevailing Cr(VI) species in solution is CrO₄ ^2?; however, CaCrO₄° and MgCrO₄° neutral complexes represent significant percentages (up to 42 %). These findings suggest that the mobility and consequently the bioavailability of Cr(VI) can be significantly enhanced by these neutral complexes, which are not considered to be affected by adsorption/desorption processes. The Cr(VI) source, investigated by means of the Mg/SiO₂ molar ratio, seems to be represented mainly by Mg-bearing minerals of the chlorite group. Petrographic observations confirm the occurrence of this mineral group. The interaction between rainwater and the local serpentinite rock was simulated at different $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ conditions by reaction path modelling using the EQ3/6 software package. $P_{{{\text{O}}_{ 2} }}$ was varied in accordance with the assumption that redox conditions are determined in part by NO₃. Results are in good agreement with experimental data on spring waters and subordinately with data on some coastal plain groundwater, which plot in a rather wide $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ field. Although the dissolved Cr content is mostly of natural origin, fertilization may affect its fate.     

Morphological effects of different channel‐forming discharges in a gravel‐bed river

The study analyses the morphological response of a gravel‐bed river to discharges of different magnitude (from moderate events that occur several times a year to a 12‐year flood) and so defines the range of formative discharges for single morphological units (channels, bars, islands) and a range of magnitude of morphological activity from the threshold discharges for gravel transport and minor bar modification up to flows causing major morphological changes. The study was conducted on the Tagliamento River, a large gravel‐bed river in north‐eastern Italy, using two different methods, analysis of aerial photographs and field observation of painted gravel particles. The available photographs (five flights from August 1997 to November 2002) and the two commissioned flights (June 2006 and April 2007) do not define periods with a single flood event, but the intervals are short enough (11 to 22 months) to have a limited number of flood events in each case. The fieldwork, which involved cross‐section survey, grain‐size analysis and observation of painted sediments, complemented the aerial surveys by allowing analysis of channel response to single flood events. Substantial morphological changes (e.g. bank erosion of several tens of metres up to more than 100 m) associated with flood events with a recurrence interval between 1·1 year and 12 years have been documented. Multiple forming discharges were defined based on the activity of different morphological units. Discharges equal to 20–50% of the bankfull discharge are formative for the channels, whereas the bankfull discharge (1·1 year flood in this case of the Tagliamento River) is formative for low bars. Larger floods, but still relatively frequent (with a recurrence interval less than five years), are required for full gravel transport on high bars and significant morphological changes of islands. Copyright © 2009 John Wiley & Sons, Ltd.     

Spatial fluctuations in the spectral shape of the ultraviolet background at 2 < z < 3 and the reionization of helium

The low-density hydrogen and helium in the intergalactic medium (IGM) probed by quasi-stellar object (QSO) absorption lines is sensitive to the amplitude and spectral shape of the metagalactic ultraviolet (UV) background. We use realistic H  i and He  ii Lyα forest spectra, constructed from state-of-the-art hydrodynamical simulations of a Λ cold dark matter (ΛCDM) universe to confirm the reliability of using line profile fitting techniques to infer the ratio of the metagalactic H  i and He  ii ionization rates. We further show that the large spatial variations and the anticorrelation with H  i absorber density observed in the ratio of the measured He  ii to H  i column densities can be explained in a model where the H  i ionization rate is dominated by the combined UV emission from young star-forming galaxies and QSOs and the He  ii ionization rate is dominated by emission from QSOs only. In such a model the large fluctuations in the column density ratio are due to the small number of QSOs expected to contribute at any given point to the He  ii ionization rate. A significant contribution to UV emission at the He  ii photoelectric edge from hot gas in galaxies and galaxy groups would decrease the expected fluctuations in the column density ratio. Consequently, this model appears difficult to reconcile with the large increase in He  ii opacity fluctuations towards higher redshift. Our results further strengthen previous suggestions that observed He  ii Lyα forest spectra at z ∼ 2–3.5 probe the tail end of the reionization of He  ii by QSOs.     

A New Population of Radio Quasars

We present a new population of radio quasars whose X-ray band, unlike previously known sources which have (flat) inverse Compton radiation, is characterized by (steep) synchrotron emission, with a broad-band spectral energy distribution similar to that of BL Lacs with high energy synchrotron peaks. We discuss how this new class was discovered, the class properties, and the implications of its existence for our understanding of jets and active galactic nuclei in general.     

Decoupled kinematics of two neighbouring permafrost creeping landforms in the Eastern Italian Alps

An overall acceleration of rock glacier displacement rates in the Alps has been observed in recent decades, with several cases of destabilization leading to potential geomorphological hazards. This behaviour has been attributed to the rising permafrost temperature, induced by atmospheric warming and regulated by thermo-hydrological processes. Landforms derived from the interaction of glacier remnants and permafrost are widespread in mountain areas, but are less studied and monitored than talus rock glaciers. This work presents a comparative study of a talus rock glacier and a glacial-permafrost composite landform (GPCL) in the Eastern Italian Alps. The two landforms are only 10 km apart, but have rather different elevation ranges and main slope aspects. The kinematics and ground thermal conditions were monitored from 2001 to 2015 along with geomorphological surveys, analyses of historical maps and remote sensing data. The dynamic behaviour of the rock glacier was similar to the majority of monitored rock glaciers in the Alps, with an acceleration after 2008 and a velocity peak in 2015. In contrast, the GPCL had a nearly unchanged displacement rate during the observation period. Statistical analyses of kinematic vs. nivo-meteorological variables revealed a dynamic decoupling of the two landforms after 2008 that corresponds with increased winter snow accumulation. Although the kinematics of both landforms respond to ground surface temperature variations, the collected evidence suggests a different reaction of ground surface temperature to variations in the precipitation regime. This different reaction is likely due to local topo-climatic conditions that affect snow redistribution by wind. The different reactions of the two systems to the same climatic forcing is likely a legacy of their different origins. GPCL dynamics result from interaction of permafrost and residual glacial dynamics that are associated with possible peculiarities in the internal/basal meltwater circulation, whose future response is uncertain and requires improved understanding. © 2019 John Wiley & Sons, Ltd. © 2019 John Wiley & Sons, Ltd.     

A generalized zero-lag cross-correlation approach for Rapid Earthquake Localization (REL): the example of the Istanbul Megacity Rapid Response System

A seismic antenna approach based on the generalized zero-lag cross-correlation method for rapid earthquake localization is proposed. This method is intended to be applied primarily for early warning, whenever the epicentre-to-target distances guarantee enough lead-time, rapid response purposes, and for those circumstances when a seismogenic area is not directly accessible with seismic stations or/and a network of instruments is concentrated within the area to be warned. The procedure we propose aims to provide useful information for magnitude determination and shake-maps generation. Indeed, it relies only on the first P-wave triggered arrivals from seismic stations, and is designed to work in real-time for the localization of events occurring outside of the network, that is, under conditions that might be detrimental to standard localization approaches. The procedure can by summarized by a few preliminary pre-seismic and real-time co-seismic steps. In the pre-seismic time-frame, for the cases where a large and dense network exists, waiting for all stations to trigger could dramatically reduce the available lead-time for the warning. Therefore, in such cases, the network could profitably be divided into sub-arrays, while also taking advantage of available earthquake recordings or simulated data sets. During the co-seismic time-frame, the main operations are: (1) individual on-site triggering by the P-wave of the seismic stations (e.g. by a STA/LTA algorithm); (2) real-time communication of key parameters (e.g. P-wave arrival time, and signal quality) to a main centre by SMS/WLAN; (3) setup of a pseudo data set, composed by a Gaussian function centred at the P-time, and with a bell width that can be set up proportional to the trigger signal-to-noise ratio (SNR); (4) calculation of a coherency map for the sub-array with triggered stations (preliminary sub-array location); and (5) stacking of coherency maps from the different sub-arrays (final location). By the stack of coherency maps estimated by the different sub-arrays in the last step of the procedure, the epicentral area’s location may be better constrained. This innovative approach for rapid localization was applied to both synthetic data, and real observations of two small earthquakes that occurred in the Marmara Sea, Turkey, which were recorded by the Istanbul Earthquake Rapid Response System.     

Three-Dimensional Mapping of Air Flow at an Urban Canyon Intersection

In this experimental work both qualitative (flow visualisation) and quantitative (laser Doppler anemometry) methods were applied in a wind tunnel in order to describe the complex three-dimensional flow field in a real environment (a street canyon intersection). The main aim was an examination of the mean flow, turbulence and flow pathlines characterising a complex three-dimensional urban location. The experiments highlighted the complexity of the observed flows, particularly in the upwind region of the intersection. In this complex and realistic situation some details of the upwind flow, such as the presence of two tall towers, play an important role in defining the flow field within the intersection, particularly at roof level. This effect is likely to have a strong influence on the mass exchange mechanism between the canopy flow and the air aloft, and therefore the distribution of pollutants. This strong interaction between the flows inside and outside the urban canopy is currently neglected in most state-of-the-art local scale dispersion models.     

Production of amorphous hydrated impure magnesium carbonate through ex situ carbonation

The evaluation of the feasibility of ex situ carbonation in landfills utilizing raw natural substances (namely serpentinites as Mg-source and the CO₂-rich fraction of biogas as C-source) was tested through a laboratory procedure comprising three steps. The first step is the acid attack of a serpentinite at 70 °C, by means of HCl 2 M, to get MgCl₂-rich solutions. Attacks of different durations were performed to evaluate the time needed. The second step is the neutralization of the MgCl₂-rich solution by addition of concentrated ammonia. The third (carbonation) step is mixing of the neutralized MgCl₂-rich solution with a solution of ammonium carbonate. This was produced in a landfill by absorption of CO₂ contained in biogas in a solution of ammonia. The neutralization of acid MgCl₂-rich solutions caused the precipitation of ferrihydrite with secondary ammonium carnallite and salammoniac, whereas abundant precipitation of Amorphous Hydrated Impure Magnesium Carbonate (AHIMC), sometimes with minor nesquehonite, occurred in the third step. This solid carbonate acts as a stable CO₂ sink up to 380 °C. The geochemical behavior of some minor elements was also investigated during the experimental processes revealing that Al, Cr and Ni were removed during neutralization (second step), in contrast to Ca which remained in the circumneutral MgCl₂-rich solution and entered into the structure of AHIMC. During the carbonation step, precipitation of artinite, hydromagnesite, lansfordite, magnesite and nesquehonite was thermodynamically impossible as the aqueous phase was undersaturated with respect to these solid phases upon separation of AHIMC.