Deterministic synthesis of Cu9S5 flakes assisted by single-layer graphene arrays.

The employment of two-dimensional materials, as growth substrates or buffer layers, enables the epitaxial growth of layered materials with different crystalline symmetries with a preferential crystalline orientation and the synthesis of heterostructures with a large lattice constant mismatch. In this work, we employ single crystalline graphene to modify the sulfurization dynamics of copper foil for the deterministic synthesis of large-area Cu9S5 crystals. Molecular dynamics simulations using the Reax force-field are used to mimic the sulfurization process of a series of different atomistic systems specifically built to understand the role of graphene during the sulphur atom attack over the Cu(111) surface. Cu9S5 flakes show a flat morphology with an average lateral size of hundreds of micrometers. Cu9S5 presents a direct band-gap of 2.5 eV evaluated with light absorption and light emission spectroscopies. Electrical characterization shows that the Cu9S5 crystals present high p-type doping with a hole mobility of 2 cm2 V-1 s-1.

Persistent warm Mediterranean surface waters during the Roman period.

Reconstruction of last millennia Sea Surface Temperature (SST) evolution is challenging due to the difficulty retrieving good resolution marine records and to the several uncertainties in the available proxy tools. In this regard, the Roman Period (1 CE to 500 CE) was particularly relevant in the socio-cultural development of the Mediterranean region while its climatic characteristics remain uncertain. Here we present a new SST reconstruction from the Sicily Channel based in Mg/Ca ratios measured on the planktonic foraminifer Globigerinoides ruber. This new record is framed in the context of other previously published Mediterranean SST records from the Alboran Sea, Minorca Basin and Aegean Sea and also compared to a north Hemisphere temperature reconstruction. The most solid image that emerges of this trans-Mediterranean comparison is the persistent regional occurrence of a distinct warm phase during the Roman Period. This record comparison consistently shows the Roman as the warmest period of the last 2 kyr, about 2 °C warmer than average values for the late centuries for the Sicily and Western Mediterranean regions. After the Roman Period a general cooling trend developed in the region with several minor oscillations. We hypothesis the potential link between this Roman Climatic Optimum and the expansion and subsequent decline of the Roman Empire.

The impact of the 1999 Mw 7.4 event in the Izmit Bay (Turkey) on anthropogenic contaminant (PCBs, PAHs and PBDEs) concentrations recorded in a deep sediment core.

The 1999 Mw 7.4 earthquake triggered a tremendous human tragedy and had a great social impact over the population of the Izmit Bay, one of the most industrialized area of Turkey. Although the successive environmental disasters were well documented, information on its sedimentary record is lacking. The present research aims at filling this gap, through the analysis of organic contaminants (PCBs, PAHs, and PBDEs) in a dated sediment core collected in the depocenter of the Karamürsel Basin in 2005. Profiles of total PCBs and total PAHs overlap the timing of industrialization in the area (starting in the 1960s) with values increasing as the population and the number of industrial plants grew larger. Profiles for PBDEs are in accordance with increasing urban inputs but are probably affected by processes of natural formation and post-depositional mixing. The continuous sedimentary record is interrupted at a level dating back to 1980 due to the erosion caused by the 1999 earthquake, having removed a 5-7cm thick sediment layer. Contaminant concentrations in the deepest 10-15cm of a 30cm thick seismo-turbidite unit, triggered by the 1999 event, increase with the progressive fining up and evidence massive transport of sediments from coastal, more polluted sites of the north-eastern Karamürsel shelves and shores. Additional inputs of PAHs are also evident, originating from a fire at the oil refinery that followed the shaking. The effects of the earthquake generated tsunami, its backwash fluxes and the following seiches are not uniquely displayed by each class of contaminants, and they could probably reflect successive inputs deriving from different parts of the basin that are subject to anthropogenic impacts of different nature. Concentrations measured at the top of the core are consistent with an unvaried input of pollutants in the period 1980-2005.

Exploring the possibility to detect recent temporal changes in highly disturbed sedimentary records through sampling repetitions and core comparisons of porosity and sand content.

Dating of sediment cores in dynamic environments (such as tropical coastal lagoons) is often impossible to achieve, due to the difficulty to recover continuous and undisturbed records. Detailed temporal definition of environmental changes cannot be assured, but there is the possibility that information retained in such sediments can still provide useful insights on local or large-scale sedimentary dynamics, when a specific strategy is adopted. This latter consists in repeated core samplings at the same location and in the comparison of core profiles for basic and easily measurable parameters (porosity and sand content). This approach was tested on sediment cores, collected repeatedly during the period 2005-2010, at the same site of the Thi Nai Lagoon (central Vietnam). The proposed procedure was able to evidence the impact on lagoon sediments of activities linked to the construction of industrial settlements in the area, with dredging removing a consistent sediment layer from 2005 to 2008 and waste dumping providing additional sediment input in the following period. Simple statistic confirmed this scenario, together with core profiles of PCBs, As, Cd, Pb, and Zn. The procedure represents a simple tool to study coastal dynamics in places where the level of accuracy of traditional sediment radiodating cannot be reached. Several ameliorations are suggested in order to help developing the monitoring of sedimentary processes in poorly studied areas.

H2A.Z-dependent crosstalk between enhancer and promoter regulates cyclin D1 expression.

H2A.Z association with specific genomic loci is thought to contribute to a chromatin structure that promotes transcription activation. Acetylation of H2A.Z at promoters of oncogenes has been linked to tumorigenesis. The mechanism is unknown. Here, we show that in triple negative breast cancer cells, H2A.Z bound to the promoter of the constitutively, weakly expressed cyclin D1 oncogene (CCND1), a key regulator of cellular proliferation. Depleting the pool of H2A.Z stimulated transcription of CCND1 in the absence of its cognate transcription factor, the estrogen receptor (ER). During activation of CCND1, H2A.Z was released from the transcription start site (TSS) and downstream enhancer (enh2) sequences. Concurrently, acetylation of H2A.Z, H3 and H4 at the TSS was increased but only H2A.Z was acetylated at enh2. Acetylation of H2A.Z required the Tip60 acetyltransferase to be associated with the activated CCND1 on both TSS and enh2 sites. Depletion of Tip60 prevented CCND1 activation. Chromosome conformation capture experiments (3C) revealed specific contacts between the TSS and enh2 chromatin regions. These results suggest that release of a histone H2A.Z-mediated repression loop activates CCND1 for transcription. Our findings open new avenues for controlling and understanding aberrant gene expression associated with tumorigenesis.

Contaminant fate and transport in the Venice Lagoon: results from a multi-segment multimedia model.

Contaminant loadings to the Venice Lagoon peaked from 1950s-1980s and although they have since declined, contaminant concentrations remain elevated in sediment and seafood. In order to identify the relative importance of contaminant sources, inter-media exchange and removal pathways, a modified 10-segment fugacity/aquivalence-based model was developed for octachlorodibenzodioxin/furan (OCDD/F), PCB-180, Pb and Cu in the Venice Lagoon. Results showed that in-place pollution nearby the industrial area, current industrial discharges, and tributary loadings were the main sources of contaminants to the lagoon, with negligible contributions from the atmosphere. The fate of these contaminants was governed by sediment-water exchange with simultaneous advective transport by water circulation. Contaminants circulated amongst the northern and central basins with a small fraction reaching the far southern basin and the Chioggia inlet. As a consequence, we estimated limited contaminant transfer to the Adriatic Sea, trapping the majority of contaminants in the sediment in this "average" circulation scenario which does not account for periodic flooding events.

Examination of the uncertainty in contaminant fate and transport modeling: a case study in the Venice Lagoon.

A Monte Carlo analysis is used to quantify environmental parametric uncertainty in a multi-segment, multi-chemical model of the Venice Lagoon. Scientific knowledge, expert judgment and observational data are used to formulate prior probability distributions that characterize the uncertainty pertaining to 43 environmental system parameters. The propagation of this uncertainty through the model is then assessed by a comparative analysis of the moments (central tendency, dispersion) of the model output distributions. We also apply principal component analysis in combination with correlation analysis to identify the most influential parameters, thereby gaining mechanistic insights into the ecosystem functioning. We found that modeled concentrations of Cu, Pb, OCDD/F and PCB-180 varied by up to an order of magnitude, exhibiting both contaminant- and site-specific variability. These distributions generally overlapped with the measured concentration ranges. We also found that the uncertainty of the contaminant concentrations in the Venice Lagoon was characterized by two modes of spatial variability, mainly driven by the local hydrodynamic regime, which separate the northern and central parts of the lagoon and the more isolated southern basin. While spatial contaminant gradients in the lagoon were primarily shaped by hydrology, our analysis also shows that the interplay amongst the in-place historical pollution in the central lagoon, the local suspended sediment concentrations and the sediment burial rates exerts significant control on the variability of the contaminant concentrations. We conclude that the probabilistic analysis presented herein is valuable for quantifying uncertainty and probing its cause in over-parameterized models, while some of our results can be used to dictate where additional data collection efforts should focus on and the directions that future model refinement should follow.

210Pb and 137Cs as chronometers for salt marsh accretion in the Venice Lagoon - links to flooding frequency and climate change.

Five salt marsh sediment cores from different parts of the Venice Lagoon were studied to determine their depositional history and its relationship with the environmental changes occurred during the past approximately 100 years. X-radiographs of the cores show no disturbance related to particle mixing. Accretion rates were calculated using a constant flux model applied to excess (210)Pb distributions in the cores. The record of (137)Cs fluxes to the sites, determined from (137)Cs profiles and the (210)Pb chronologies, shows inputs from the global fallout of (137)Cs in the late 1950s to early 1960s and the Chernobyl accident in 1986. Average accretion rates in the cores are comparable to the long-term average rate of mean sea level rise in the Venice Lagoon ( approximately 0.25 cm y(-1)) except for a core collected in a marsh presumably affected by inputs from the Dese River. Short-term variations in accretion rate are correlated with the cumulative frequency of flooding, as determined by records of Acqua Alta, in four of the five cores, suggesting that variations in the phenomena causing flooding (such as wind patterns, storm frequency and NAO) are short-term driving forces for variations in marsh accretion rate.

Polychlorinated biphenyls in sediments of the Tam Giang-Cau Hai Lagoon, Central Vietnam.

The Tam Giang-Cau Hai Lagoon, the largest in south east Asia, suffers from a great anthropogenic pressure and appears subject to a process of progressive environmental deterioration. To establish causes, history and trends of lagoon contamination, sediment samples representing three major parts of the systems were sampled and analysed for porosity, organic carbon, total nitrogen, delta(13)C, grain size, radiotracers and PCBs. PCB surficial concentrations range from 10.2 to 24.5 microg kg(-1), and maximum values are close to NOAA ERL guidelines. The downcore distribution of PCBs shows two well defined peaks in the core from Tam Giang (25.5 and 16.2 microg kg(-1)), whereas the sediment from Cau Hai is characterised by a maximum at the surface. Therefore, present trends indicate that contamination is still increasing or slightly decreasing. The prevailing congeners are 3-CB and 4-CB, hence recent PCBs appear to be mostly originated by Aroclor 1016- and 1242-like mixtures, with some samples influenced also by Aroclor 1248. Present sources seem to be similar everywhere and probably they are widespread all over the territory of the Thua Thien-Hue province.

Accumulation of polychlorinated biphenyls in sediments of the Venice Lagoon and the industrial area of Porto Marghera.

Sediment cores, collected at seven sites in the Venice Lagoon and within the canals of the industrial area were analyzed for polychlorinated biphenyls (PCBs) in order to assess the chronology of pollution and its present trends. The surficial concentration of PCBs is very high (more than 2049 microg kg(-1)) only in the Brentella Canal, probably due to a very recent contaminating episode. Very high values downcore (up to 41,639 microg kg(-1)) can be found in different parts of the industrial area, especially in the canals Lusore-Brentelle and Salso. Lagoon samples are much less contaminated (2.7-123 microg kg(-1)), being influenced only occasionally by polluted sediments resuspended from the canals. Sediment chronology shows that the delivery of contaminants peaked in the 1970s-early 1980s, decreasing since at most sites. Congener profiles distinguish PCBs in two main categories: heavy congeners characterize a baseline pollution, probably due to a large variety of sources within the lagoon system, whereas a mixture of light PCBs was discharged into the canals Brentella and Salso.

Accumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans in sediments of the Venice Lagoon and the industrial area of Porto Marghera.

Two sediment cores collected from the central Venice Lagoon and five from the canals of the nearby industrial area were studied in order to assess the temporal evolution of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) delivery and present trends. The most polluted site is C12, in the Brentella Canal, with a total equivalent (TEQ) concentration of 2858 and 64,130 ng kg-1 at the surface and at 18-20 cm depth, respectively. High values can be also found in the Nord Industrial Canal and in the Salso Canal: 3000 and 2500 ng kg-1, respectively. Lagoon samples are much less contaminated, with TEQ downcore maxima of 22 and 53 ng kg-1, being influenced by pollutants stored in sediments of the canals only occasionally. Sediment chronology, based on 210Pb and 137Cs activity-depth profiles, shows that the highest fluxes occurred in the 1970s and early 1980s, and that pollution is now decreasing. Homologue profiles can distinguish PCDD/Fs from different sources: combustion for octachlorinated dibenzo-p-dioxin (OCDD) and stripping of VCM for octachlorinated dibenzofuran (OCDF) alone, whereas several activities carried out in the past within the industrial area can be responsible of the overall contamination by furans.

Polychlorinated biphenyls in sediments of the Venice Lagoon.

Twenty-four surficial sediment samples, representing different environments within the Venice Lagoon, were analyzed for polychlorinated biphenyls (PCBs) in order to assess degrees of pollution, sources, areal distribution, and potential risk for the environment. Concentrations in surficial sediments range from 2 to more than 2049 microg kg(-1) dw. The maximum is probably due to the discharge of industrial wastes into the Brentella Canal, within the first Industrial Area. Lagoon samples are 11-205 times less contaminated, being influenced by pollutants stored in the canals only occasionally. Congener profiles distinguish PCBs in two main categories. The baseline pollution is probably due to a variety of sources within the lagoon system, whereas less chlorinated PCBs were discharged into the Brentella Canal. Our estimates suggest that, due to high concentrations, toxic equivalents (TEQs) of PCBs are comparable to those relative to PCDD/Fs for the least contaminated samples, whereas they are lower in case of heavy PCDD/F contamination.

Sediment composition and normalisation procedures: an example from a QUASH project sediment exercise.

The QUASH UE-Project was designed to assess the reliability of normalisation approaches to compensate the influence of natural process affecting the distribution and concentration of contaminants in sediment. The focus of this paper was to test the influence on normalisation procedures of an inorganic matrix using a sample collected in the Venice Lagoon, Italy.

Intracellular concentrations of fura-2 and fura-2/am in vascular smooth muscle cells following perfusion loading of fura-2/am in arterial segments.

A new method for the determination of tissue concentrations of Fura-2 and Fura-2/AM was developed based upon acetonitrile extraction followed by RP-HPLC separation (using tetrahexylammonium as counter-ion), post-column alkaline hydrolysis of Fura-2/AM, and fluorimetric detection. The detection limit was 1.2 nM and 1 nM for Fura-2 and Fura-2/AM, respectively. When this technique was applied to perfusion-loaded segments of the rat tail artery, intracellular concentrations of Fura-2 determined by tissue disruption were 10 times those obtained by comparing the increase in fluorescence at the isoemissive point (following loading), with a calibration curve for Fura-2. Loading conditions of 90 min at [Fura-2/AM]e = 5 microM were optimal in terms of [Fura-2]i which attained a concentration not significantly different from [Fura-2/AM]e. Under such conditions, however, Fura-2/AM also accumulated in the arterial wall. Although incompletely de-esterified, Fura-2/AM metabolites produced by in vitro incubation of Fura-2/AM with pig liver esterases could be easily detected, fluorescent forms of Fura-2 with a different sensitivity for calcium were not detected in arterial extracts.

[Description of an accident in the Carrara marble mines]. / Descrizione di un caso di infortunio nelle cave di marmo di Carrara.

New technological systems introduced in marble quarries have increased production but also the risk of accidents among the workforce. A case of an unusual accident is described that occurred in the marble quarries of Carrara (Italy) which we believe will be of interest to occupational health professionals in view of its medical and legal implications.