High‐resolution synchrotron X‐ray fluorescence investigation of calcite coralloid speleothems: Elemental incorporation and their potential as environmental archives

Synchrotron high‐resolution and micro‐X‐ray fluorescence elemental mapping of two coeval coralloid speleothems from Lamalunga Cave (Italy) are complemented with petrographic, morphological and microstratigraphic studies. The importance of these speleothems relies on their direct and indirect association with a complete Neanderthal skeleton (‘Altamura Man’) found inside the cave. The coralloids grew discontinuously between 64·6 ka and the Holocene and reveal exceptionally high concentrations of Mg, Sr and Si, particularly on convex surfaces, where evaporation is more intense. The incorporation of trace elements depends on several factors including location, shape and geometrical evolution during their growth, as well as climate and environmental parameters. This resulted in calcite precipitation with Sr compositions from 100 to 1200 ppm and an average concentration of 7000 ppm Mg. An unusually high Si content (up to 16%) is possibly derived from volcanic ash transported as particulate and in solution inside the cave. The most common fabrics observed consist of non‐fluorescent elongated columnar calcite forming clean isopachous bands and fluorescent fibre‐like crystals associated with laminated, lenticular bands high in Sr, Mg and Si. Variability in Sr, Mg and Si concentrations appears to induce fabric changes in the coralloids. Elongation and lattice distortion of the crystals was found to coincide with high Mg concentrations. The transition from compact elongated to open to fibre‐like, is here interpreted as due to high concentrations of Si and Sr, which are preferentially incorporated in the speleothem at crystal boundaries and intra‐laminae. It is here inferred that coralloid fabric changes and their elemental content potentially record local rainfall variations through time, with the clean compact calcite marking high infiltration and open fibre‐like and micrite fabrics recording dry periods.     

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2+/-0.7-4.0+/-0.5; relative penis length: 6-47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs=43+/-14 ngSng(-1)w.) were significantly lower than in the other stations (range of average sum of BuTs: 101+/-22-217+/-27 ngSng(-1)d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r=0.95, n=8, p<0.05.     

Confidence interval of real‐time forecast stages provided by the STAFOM‐RCM model: the case study of the Tiber River (Italy)

This study proposes a statistically based procedure to quantify the confidence interval (CI) to be associated to the stages forecast by a simple model called STAge FOrecasting Model‐Rating Curve Model (STAFOM‐RCM). This model can be used for single river reaches characterized by different intermediate drainage areas and mean wave travel times when real‐time stage records, cross section surveys and rating curves are available at both ends. The model requires, at each time of forecast, an estimate of the lateral contribution q_for between the two sections delimiting the reach. The CI of the stage is provided by analyzing the statistical properties of model output in terms of lateral flow, and it is derived from the CI of the lateral contribution q_for which, in turn, is set up by associating to each q_for the q_opt which allows STAFOM‐RCM to reproduce the exact observed stage. From an operative point of view, the q_for values are ranked in order of magnitude and subdivided in classes where the q_opt values can be represented through normal distributions of proper mean and variance from which an interval of selected confidence level for q_for is computed and transferred to the stage. Three river reaches of the Tiber river, in central Italy, are used as case study. A sensitivity analysis is also performed in order to identify the minimum calibration set of flood events. The CIs obtained are consistent with the level of confidence selected and have practical utility. An interesting aspect is that different CI widths can be produced for the same forecast stage since they depend on the estimate of q_for made at the time of forecast. Overall, the proposed procedure for CI estimate is simple and can be conveniently adapted for other forecasting models provided that they have physically based parameters which need to be updated during the forecast. Copyright © 2012 John Wiley & Sons, Ltd.     

A relocatable ocean model in support of environmental emergencies

During the Costa Concordia emergency case, regional, subregional, and relocatable ocean models have been used together with the oil spill model, MEDSLIK-II, to provide ocean currents forecasts, possible oil spill scenarios, and drifters trajectories simulations. The models results together with the evaluation of their performances are presented in this paper. In particular, we focused this work on the implementation of the Interactive Relocatable Nested Ocean Model (IRENOM), based on the Harvard Ocean Prediction System (HOPS), for the Costa Concordia emergency and on its validation using drifters released in the area of the accident. It is shown that thanks to the capability of improving easily and quickly its configuration, the IRENOM results are of greater accuracy than the results achieved using regional or subregional model products. The model topography, and to the initialization procedures, and the horizontal resolution are the key model settings to be configured. Furthermore, the IRENOM currents and the MEDSLIK-II simulated trajectories showed to be sensitive to the spatial resolution of the meteorological fields used, providing higher prediction skills with higher resolution wind forcing.     

A contribution to the reconstruction of Miocene seepage from authigenic carbonates of the northern Apennines (Italy)

Authigenic carbonates from outcrops of the northern Apennines consist of small and irregular lenses and exhibit numerous features indicative of cold-seep settings. Detailed petrographic, mineralogical and geochemical studies from two Miocene deposits are presented. The first carbonate outcrop, named Fosso Riconi, is located in the foredeep basin of the Apenninic chain, whereas the second deposit represents a satellite basin called Sarsetta. The stable isotope data from specific carbonate minerals show a wide range of values well known from other palaeoseeps of the Apennine Mountains. The majority of seep carbonates are formed by low-Mg calcite and ankerite. Those minerals have δ¹³C values between ?7 and ?23‰ V-PDB, suggesting variable amounts of carbonate derived from oxidized methane, seawater (dissolved inorganic carbon) and sedimentary organic matter. Dolomite samples have the lowest δ¹³C values (?30.8 to ?39.0‰ V-PDB), indicating methane as the main carbon source. The findings suggest an evolutionary formation of the seeps and development of authigenic carbonates influenced by the activity of chemosynthetic organisms, of which large lucinid clams are preserved. Bioirrigation by the clams controlled the sediment–water exchange, and is here considered as an explanation for the anomalous Mg content of the calcite. We hypothesize that the seep carbonates were formed during periods of active methane-rich seepage, whereas during periods of slow seepage carbonate formation was reduced. Despite different geological settings, the two examined deposits of Sarsetta and Fosso Riconi show similar features, suggesting that a common pattern of fluid circulation played a major role in carbonate formation at both seep sites.     

Temporal correlations and clustering of landslides

This paper examines temporal correlations and temporal clustering of a proxy historical landslide time series, 2255 reported landslides 1951–2002, for an area in the Emilia‐Romagna Region, Italy. Landslide intensity is measured by the number of reported landslides in a day (D_L) and in an ‘event’ (S_event) of consecutive days with landsliding. The non‐zero values in both time series D_L and S_event are unequally spaced in time, and have heavy‐tailed frequency‐size distributions. To examine temporal correlations, we use power‐spectral analysis (Lomb periodogram) and surrogate data analysis, confronting our original D_L and S_event time series with 1000 shuffled (uncorrelated) versions. We conclude that the landslide intensity series D_L has strong temporal correlations and S_event has likely temporal correlations. To examine temporal clustering in D_L and S_event, we consider extremes over different landslide intensity thresholds. We first examine the statistical distribution of interextreme occurrence times, τ, and find Weibull distributions with parameter γ << 1·0 [D_L] and γ < 1·0 [S_event]; thus D_L and S_event each have temporal correlations, but S_event to a lesser degree. We next examine correlations between successive interextreme occurrence times, τ. Using autocorrelation analysis applied to τ, combined with surrogate data analysis, we find for D_L linear correlations in τ, but for S_event inconclusive results. However, using Kendall's rank correlation analysis we find for both D_L and S_event the series of τ are strongly correlated. Finally, we apply Fano Factor analysis, finding for both D_L and S_event the timings of extremes over a given threshold exhibit a fractal structure and are clustered in time. In this paper, we provide a framework for examining time series where the non‐zero values are strongly unequally spaced and heavy‐tailed, particularly important in the Earth Sciences due to their common occurrence, and find that landslide intensity time series exhibit temporal correlations and clustering. Many landslide models currently are designed under the assumption that landslides are uncorrelated in time, which we show is false. Copyright © 2010 John Wiley & Sons, Ltd.     

SWASV speciation of Cd, Pb and Cu for the determination of seawater contamination in the area of the Nicole shipwreck (Ancona coast, Central Adriatic Sea)

The study reports for the first time on the heavy metal contamination of the waters surrounding a shipwreck lying on the sea floor. Square wave anodic stripping voltammetry has been used for a survey of the total and dissolved Cd, Pb and Cu contents of the seawater at the site of the sinking of the Nicole M/V (Coastal Adriatic Sea, Italy). Results show that the hulk has a considerable impact as regards all three metals in the bottom water, especially for the particulate fraction concentrations, which increased by factors of ∼9 (Cd), ∼3 (Pb) and ∼5 (Cu). The contaminated plume extended downstream for about 2 miles. Much lower contamination was observed for dissolved bottom concentrations; nevertheless Pb (0.56 ± 0.03 nmol/L) is higher than the Italian legal limits established for 2015 and Cd (0.23 ± 0.03 nmol/L) is very close the limit of Cd will be exceeded if the hulk is not removed.     

The Effect of Velocity Inversions on H/V

We analyzed the phenomenology of microtremor H/V curves under inversions in the shear-wave velocity (V_s) profile in the subsoil. Under no V_s inversion the spectral signature of the H/V peaks is found to be ‘eye-shaped’ with the horizontal components higher than the vertical. Conversely, under negative velocity gradients, numerous of differences emerge. I) A H/V ratio below 1 is observed for a wide range of frequencies, due to the decrease of the horizontal components below the vertical one. II) In the presence of persistent H/V < 1, small bumps in the H/V ratio given by local minima in the vertical spectral component may represent the relics of the peaks indicating resonances and stratigraphic discontinuities. As a consequence, in the presence of velocity inversions the H/V > 2 SESAME (2004) criterion fails but a stratigraphic interpretation may still be possible. III) The H/V curves should always be interpreted together with the single component spectra. IV) Microtremor H/V measurements for stratigraphic/microzonation purposes on stiff artificial soils, (asphalt, concrete, cement, pavements) should always be avoided since the latter often produce velocity inversions. This may have consequences in the intermediate to high frequency domain ( > 1 Hz) also in the application of reference site methods, like H_site/H_bedrock, to microtremor. Theoretical modeling confirms these experimental findings.     

Constraints on the Palaeoproterozoic tectono-metamorphic evolution of the Lewisian Gneiss Complex,NW Scotland: Implications for Nuna assembly

Despite extensive investigation, the tectono-thermal evolution of the Archean crust in the Lewisian Gneiss Complex in NW Scotland (LGC) is debated. Most U–Pb zircon geochronological and metamorphic studies have focused on rocks from the central region of the mainland LGC, where granulite facies assemblages associated with the oldest (Badcallian) tectono-metamorphic event at c. 2.75 Ga are overprinted by younger amphibolite facies assemblages related to the Inverian (c. 2.5 Ga) and subsequent Laxfordian (c. 1.9–1.65 Ga) tectono-thermal events. In the southern and northern regions of the mainland LGC, deformation and metamorphism associated with the Laxfordian event are pervasive, although the timing and conditions are poorly constrained. Here, we present new field, petrographic and structural data, U–Pb zircon and titanite geochronology and phase equilibrium modelling of amphibolite samples from the northern and southern regions. Our field observations show that in both regions, pre-Laxfordian structures are significantly reworked by steep NW-striking fabrics that are themselves pervasively overprinted by co-axial deformation and amphibolite facies metamorphism related to the Laxfordian event. In situ U–Pb titanite geochronology yields Laxfordian ages of 1853 ± 20 Ma in the southern region (P = 6–8 kbar and T = 640–690°C) and 1750 ± 20 Ma and 1776 ± 10 Ma in the northern region (P = 6–7.5 kbar and T = 740–760°C). While U–Pb dating of zircon rims from felsic gneisses in the central region shows a dominant Inverian metamorphic overprint at c. 2500 Ma, zircon rims in felsic gneisses from the northern and southern regions commonly yield Laxfordian dates as young as c. 1800 Ma. Combined, the results support the idea that, during the Palaeoproterozoic, the central region of the LGC acted as low-strain domain, in which intense deformation and metamorphism were restricted to crustal-scale shear zones. By contrast, in the southern and northern regions, early (c. 1.85 Ga) and late (c. 1.75 Ga) Laxfordian deformation and fluid-mediated metamorphism were much more pervasive and at higher P–T conditions than previously proposed. The diachronous Laxfordian evolution of the southern and northern regions indicate that they reflect early and late snapshots of collisional to transpressional tectonics in the mainland LGC. The long-lasting Laxfordian evolution documents the collision of the Rae and North Atlantic cratons during the Palaeoproterozoic amalgamation of the supercontinent Nuna, with implications for the palaeogeographic configuration of NW Scotland during Palaeoproterozoic Nuna.