The key role played by the Augusta basin (southern Italy) in the mercury contamination of the Mediterranean Sea

The Augusta basin, located in SE Sicily (southern Italy), is a semi-enclosed marine area, labelled as a highly contaminated site. The release of mercury into the harbour seawater and its dispersion to the blue water, make the Augusta basin a potential source of anthropogenic pollution for the Mediterranean Sea. A mass balance was implemented to calculate the HgT budget in the Augusta basin. Results suggest that an average of ～0.073 kmol of HgT is released, by diffusion, on a yearly basis, from sediments to the seawater, with a consequent output of 0.162 kmol y(-1) to coastal and offshore waters; this makes the Augusta area an important contributor of mercury to the Mediterranean Sea. Owing to the geographical location of the Augusta basin, its outflowing shelf-waters are immediately intercepted by the surface Atlantic Ionian Stream (AIS) and mixed with the main gyres of the eastern Mediterranean Sea, thus representing a risk for the large-scale marine system.     

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from Italian women living in Rome and Venice

The levels of selected polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in human milk samples from the areas of Venice and Rome, primarily in order to characterize the current levels of infant exposure to PCBs and PBDEs due to breast feeding in Italy. Sixteen non-dioxin-like PCBs, including the traditional indicator congeners, and 11 PBDEs, comprising the relevant PBDE-47, PBDE-99, and PBDE-153, were determined. Congeners were selected for analysis according to their relative abundance in human tissues, toxicological relevance, and diffusion in the environment. Dietary habits of the milk donors were recorded by questionnaires; mothers of the Venice area were classified into three groups according to their consumption of local fish, molluscs, and other fishery products. Sigma(16)(PCBs) and Sigma(11)(PBDEs) (ng g(-1) fat) for the areas of Venice and Rome were respectively, 250-390 and 240, and 1.6-2.8 and 4.1. An increase of fish and fishery product consumption could not be associated with an increase of PCB and PBDE levels in milk.     

Particulate matter in the indoor and outdoor air of a gymnasium and a fronton

An indoor/outdoor monitoring programme of PM₁₀ was carried out in two sports venues (a fronton and a gymnasium). Levels always below 50 μg m^?3 were obtained in the fronton and outdoor air. Due to the climbing chalk and the constant process of resuspension, concentrations above 150 μg m^?3 were registered in the gymnasium. The chalk dust contributed to CO₃ ^2? concentrations of 32?±?9.4 μg m^?3 in this sports facility, which represented, on average, 18 % of the PM₁₀ mass. Here, the carbonate levels were 128 times higher than those registered outdoors. Much lower concentrations, around 1 μg m^?3, were measured in the fronton. The chalk dust is also responsible for the high Mg²⁺ concentrations in the gym (4.7?±?0.89 μg m^?3), unfolding a PM₁₀ mass fraction of 2.7 %. Total carbon accounted for almost 30 % of PM₁₀ in both indoor spaces. Aerosol size distributions were bimodal and revealed a clear dependence on physical activities and characteristics of the sports facilities. The use of climbing chalk in the gymnasium contributed significantly to the coarse mode. The average geometric mean diameter, geometric standard deviation and total number of coarse particles were 0.77 μm, 2.79 cm^?3 and 28 cm^?3, respectively.     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Black layers on historical architecture

Background, aim and scope

The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called ‘black crusts’. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider ‘black crusts’ all similar, whilst only a careful diagnostic investigation can distinguish ‘black crusts’ and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out.

Materials and methods

Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy.

Results

Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay.

Discussion

The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in ‘recent’ crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out.

Conclusions

In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past.

Recommendations and perspectives

New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.     

Spatial patterns and autocorrelation in the response of microarthropods to soil pollutants: The example of oribatid mites in an abandoned mining and smelting area

Although exogenous factors such as pollutants can act on endogenous drivers (e.g. dispersion) of populations and create spatially autocorrelated distributions, most statistical techniques assume independence of error terms. As there are no studies on metal soil pollutants and microarthropods that explicitly analyse this key issue, we completed a field study of the correlation between Oribatida and metal concentrations in litter, organic matter and soil in an attempt to account for spatial patterns of both metals and mites. The 50-m wide study area had homogenous macroscopic features, steep Pb and Cu gradients and high levels of Zn and Cd. Spatial models failed to detect metal–oribatid relationships because the observed latitudinal and longitudinal gradients in oribatid assemblages were independent of the collinear gradients in the concentration of metals. It is therefore hypothesised that other spatially variable factors (e.g. fungi, reduced macrofauna) affect oribatid assemblages, which may be influenced by metals only indirectly.     

Methane oxidation and attenuation of sulphur compounds in landfill top cover systems: Lab-scale tests

In this study,a top cover system is investigated as a control for emissions during the aftercare of new landfills and for old landfills where biogas energy production might not be profitable.Different materials were studied as landfill cover system in lab-scale columns:mechanical–biological pretreated municipal solid waste(MBP);mechanical–biological pretreated biowaste(PB);fine(PBS_f)and coarse(PBS_c)mechanical–biological pretreated mixtures of biowaste and sewage sludge,and natural soil(NS).The effectiveness of these materials in removing methane and sulphur compounds from a gas stream was tested,even coupled with activated carbon membranes.Concentrations of CO_2,CH_4,O_2,N_2,H_2S and mercaptans were analysed at different depths along the columns.Methane degradation was assessed using mass balance and the results were expressed in terms of methane oxidation rate(MOR).The highest maximum and mean MOR were observed for MBP(17.2 g CH_4/m~2/hr and 10.3 g CH_4/m~2/hr,respectively).Similar values were obtained with PB and PBS_c.The lowest values of MOR were obtained for NS(6.7 g CH_4/m~2/hr)and PBS_f(3.6 g CH_4/m~2/hr),which may be due to their low organic content and void index,respectively.Activated membranes with high load capacity did not seem to have an influence on the methane oxidation process:MBP coupled with 220 g/m~2and 360 g/m~2membranes gave maximum MOR of 16.5 g CH_4/m~2/hr and 17.4 g CH_4/m~2/hr,respectively.Activated carbon membranes proved to be very effective on H_2S adsorption.Furthermore,carbonyl sulphide,ethyl mercaptan and isopropyl mercaptan seemed to be easily absorbed by the filling materials.     

Intensity of land use changes in a sugarcane expansion region,Brazil

In the last decades, Brazil has been consolidated as one of the world’s largest producers of food, with emphasis on soybeans, sugarcane and beef production. With the opening of new markets and the increase in demand, a competitive scenario was developed among farming activities, resulting in changes in land use and cover. Thus, this study aimed to verify the spatial and temporal land use changes, through intensity analysis, in the microregion of Presidente Prudente, São Paulo state, in two time intervals, 2004–2007 and 2007–2015, in addition to determining the relevance of pasture in this context. The identification of land uses occurred through the analysis of the spectrum-temporal pattern of the Normalized Difference Vegetation Index (NDVI) from Moderate-Resolution Imaging Spectroradiometer (MODIS), in such a way that six classes were identified, annual crop, water, sugarcane, forest, pasture and urban area. The categories annual crop and sugarcane had more intense variations of losses and gains in the studied time intervals. The category pasture was the primary supplying source of the area, showing a reduction of approximately 180,000 hectares in the analyzed period, losing area with greater intensity for the categories of annual crop and sugarcane.     

Trophic importance of subtidal metazoan meiofauna: evidence from in situ exclusion experiments on soft and rocky substrates

In coastal marine ecosystems, predation might affect spatial distribution and population dynamics of benthic assemblages. Here, by means of experimental exclusion of potential predators, we compared the effects of epibenthic predation on metazoan meiofaunal assemblages on soft and rocky substrates. Different patterns of abundance were observed in uncaged versus caged plots, across habitats. In caged soft substrates, the abundance of Nematodes, Copepods and Polychaetes increased by 56, 45, 57%, respectively, in the first 3 months. An increase in the number of meiofaunal taxa was also observed. The exclusion of predators from rocky substrates showed less clear patterns. It did not affect the number of taxa while a decrease in meiofaunal abundance was observed. Our results suggest that the exclusion of epibenthic predators had clear effect on total metazoan meiofaunal abundance and on the number of taxa, only in soft bottoms. The different impact of predation across habitats can be potentially explained by differences in terms of spatial variability and substrate complexity. We estimated that, coarsely, more than 75% of total metazoan meiofaunal production can be channeled to higher trophic levels through predation on soft-bottoms. Among meiofaunal taxa, Polychaetes and Nematodes provided the major contribution to benthic energy transfers. These results suggest the trophic relevance of metazoan meiofauna in coastal food webs and claim for the refinement of further experiments for the quantification of its role in different ecological systems.     

An integrated GIS for sedimentological and geomorphological analysis of a lagoon environment. Barra de Cananéia inlet region, (Southeastern Brazil)

The aim of this work is to use GIS integration data to characterize sedimentary processes in a SubTropical lagoon environment. The study area was the Cananéia Inlet estuary in the southeastern section of the Cananéia Lagoon Estuarine System (CLES), state of S?o Paulo, Brazil (25°03′S/47°53′W). The area is formed by the confluence of two estuarine channels forming a bay-shaped water body locally called “Trapandé Bay”. The region is surrounded by one of the most preserved tracts of Atlantic Rain Forest in Southwestern Brazil and presents well-developed mangroves and marshes. In this study a methodology was developed using integrated a GIS database based on bottom sediment parameters, geomorphological data, remote sensing images, Hidrodynamical Modeling data and geophysical parameters. The sediment grain size parameters and the bottom morphology of the lagoon were also used to develop models of net sediment transport pathways. It was possible to observe that the sediment transport vectors based on the grain size model had a good correlation with the transport model based on the bottom topography features and Hydrodynamic model, especially in areas with stronger energetic conditions, with a minor contribution of finer sediments. This relation is somewhat less evident near shallower banks and depositional features. In these regions the organic matter contents in the sediments was a good complementary tool for inferring the hydrodynamic and depositional conditions (i.e. primary productivity, sedimentation rates, sources, oxi-reduction rates).