Fluorine in the rocks and sediments of volcanic areas in central Italy: total content, enrichment and leaching processes and a hypothesis on the vulnerability of the related aquifers

Rock, sediment and water samples from areas characterised by hydrothermal alterations in the Sabatini and Vico Volcanic Districts, near Rome and the large city of Viterbo, respectively, were collected and analysed to determine the total fluorine (F) content and to understand the F geochemical background level in the volcanic districts of central Italy. Leaching and alteration processes controlling the high concentration of F in water were also investigated. Fluorine concentrations were directly determined (potentiometrically) by an F selective electrode in water samples, while the procedure for rock samples included preliminary F dissolution through alkaline fusion. F concentrations higher than 800 mg kg(-1) were commonly found in the analysed rocks and sediments; the concentration depended on the lithology and on the distance from the alteration areas. A specific successive sampling campaign was conducted in three areas where the F content in sediments was particularly high; in the same areas, measurements of CO(2) flux were also performed to investigate the possible deep origin of F. To verify the relationships among the high F contents in rocks and sediments, the leaching processes involved and the presence of F in the aquifer, we also collected water samples in the western sector of the Sabatini Volcanic District, where hydrothermal manifestations and mineral springs are common. The data were processed using a GIS system in which the F distribution was combined with morphological and geological observations. The main results of our study are that (1) F concentrations are higher in volcanic and recently formed travertine (especially in hydrothermally altered sediments) than in sedimentary rocks and decrease with distance from hydrothermal alteration areas, (2) F is more easily leached from hydrothermally altered rocks and from travertine and (3) sediments enriched with F may indicate the presence of deep regional fractures that represent direct pathways of hydrothermal fluids from the crust to the surface.     

Minimum Quality Standards in Hedonic Markets with Environmental Externalities

We investigate the introduction of a minimum quality standard (MQS) in a vertically differentiated duopoly with an environmental externality. We establish that the MQS bites only if the hedonic component of consumer preferences is sufficiently strong. Then, we illustrate an underlying trade-off between the beneficial effects of quality enhancement on prices and the associated undesirable increase in the environmental externality.     

Exploring the utility of <Emphasis Type="Italic">Posidonia oceanica</Emphasis> chlorophyll fluorescence as an indicator of water quality within the European Water Framework Directive

The European Water Framework Directive commits partner countries to evolve uniform protocols for monitoring the environmental condition of natural water bodies, crucially integrating biological and ecological criteria from the associated ecosystems. This has encouraged considerable research on the development of bioindicator-based systems of water quality monitoring. A critical step towards this end is providing evidence that the proposed bioindicator system adequately reflects the human pressures to which a specific water body is submitted. Here we investigate the utility of pulse-amplitude-modulated (PAM) fluorometry, a fast, non-destructive and increasingly popular bioindicator-based method, in assessing water quality based on the widespread Mediterranean seagrass Posidonia oceanica, an important constituent of submersed benthic vegetation. Specifically, we evaluated the ability of PAM to discriminate between sites along a pre-established gradient of anthropogenic pressures and the consistency and reliability of PAM parameters across spatial scales. Our results show that the maximum quantum yield (Fv/Fm), representing the structural photosynthetic efficiency of the plant, responds significantly to the degree of site-level anthropogenic pressure. However, Fv/Fm values in our study increased with increasing pressure, in striking contrast with other studies that report declines in Fv/Fm values with increasing stress. A potential explanation for this discrepancy is that our study sites were influenced by multiple diffuse stressors (characteristic of most coastal waters) that could potentially interact with each other to influence Fv/Fm values in often unpredictable ways. The photosynthetic variables calculated from rapid light curves (ETR_max, maximum electron transport rate; α, initial slope of the curve; I _k, saturating irradiance), which represent an instant picture of the photosynthetic activity of the plant, were unable to clearly discriminate between sites subject to different anthropogenic pressures due to considerable small-scale variability. Taken together, these results suggest that even though PAM fluorometry may be a good candidate tool for monitoring water bodies in terms of costs and applicability, considerably more needs to be understood about how its parameters respond to real-world stressors, particularly when they act in concert with each other. With our present understanding of seagrass photosynthetic responses to anthropogenic stress, it would be ill advised to employ PAM as anything but a complementary tool to validate environmental stress derived with other, more robust methodologies.     

Analysis of the air pollution climate at a central urban background site

Measurements of air pollutants from a background site in central London are analysed. These comprise hourly data for CO, NO, NO₂, O₃, SO₂ and PM₁₀ from 1996 to 2008 and particle number count from 2001 to 2008. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and autocorrelation and cross-correlation functions. CO, NO and NO₂ show a typical traffic-associated pattern with two daily peaks and lesser concentrations at the weekend. Particle number count and PM₁₀ show a similar cycle, but with smaller amplitude. Ozone has an annual cycle with a maximum in May, influenced by the spring maximum in background ozone, but the diurnal and weekly cycles are dominated by losses through reaction with nitric oxide. Particle number count shows a minimum corresponding with maximum air temperatures in August, whereas the CO, NO NO₂ and SO₂ show a minimum in June/July. There is a lower particle count to NO_x ratio at the background site compared to a central London kerbside site (Marylebone Road) and a seasonal pattern in particle count to NO_x and PM₁₀ ratios consistent with loss of nanoparticles by evaporation during atmospheric transport. Sulphur dioxide peaks in the morning in summer, but at midday in winter consistent with emissions from elevated sources mixing down from aloft as the diurnal mixed layer deepens. Implications for epidemiological studies of air quality and health are discussed. Sulphur dioxide, carbon monoxide, nitric oxide and nitrogen dioxide show clear downward trends over the measurement period, PM₁₀ declines initially before levels stabilised, and ozone concentrations increased.     

Ambient monitoring of asbestos in selected Italian living areas

This paper presents the results of an intensive monitoring activity of the particulate, fall-out and soil of selected living areas in Italy with the aim to detect the asbestos concentration in air and subsequent risk of exposure for the population in ambient living environments, and to assess the nature of the other mineral phases composing the particulate matrix. Some areas were sorted out because of the presence of asbestos containing materials on site whereas others were used as blank spots in the attempt to detect the background environmental concentration of asbestos in air. Because the concentration of asbestos in ambient environments is presumably very low, and it is well known that conventional low–medium flow sampling systems with filters of small diameter (25 mm) may collect only a very small fraction of particulate over a short period, for the first time here, an intense monitoring activity was conducted with a high flow sampling system. The high flow system requires the use of large cellulose filters with the advantage that, increasing the amount of collected dust, the probability to collect asbestos fibers increases. Both the protocol of monitoring and analysis are novel and prompted by the need to increase the sensitivity towards the small number of expected fibers. With this goal, the collection of fall-out samples (the particulate falling into a collector filled with distilled water during the monitoring shift) and soil samples was also accomplished. The analytical protocol of the matrix particulate included preliminary X-ray powder diffraction (XRPD), optical microscopy and quantitative electron microscopy (SEM and TEM). Correlations with climatic trends and PM10 concentration data were also attempted.The surprising outcome of this work is that, despite the nature of the investigated site, the amount of dispersed asbestos fibers is very low and invariably lower than the theoretical method detection limits of the SEM and TEM techniques for identification and counting of asbestos fibers. The results are compared to the literature data worldwide and an updated model for asbestos fibers dispersion in ambient environments is proposed.     

Production of Ethanol by an Integrated Valorization of Olive Oil Byproducts. The Role of Phenolic Inhibition (2 pp)

Background, Aim and Scope Agricultural industrial wastes can frequently be used as raw materials in the production of bio-fuels. Olive-oil milling wastewater is considered as one of the most polluting agro-industrial residues, but fortunately due to its high content of organic matter, it has the potential to be a valuable starting material to obtain bio-ethanol via fermentation with Saccharomyces cerevisiae. The fermentation of olive-oil milling wastewater has been demonstrated with good yield of ethanol (8-12%v/v) once the level of reducing sugars is appropriate and the phenolic fraction, which inhibits the yeast, is removed. Materials and Methods: - Results: - Discussion: - Conclusions: - Recommendations and Perspectives: -     

High concern chemicals in top layer sediments of the northern Adriatic seabed as markers of old waste dumpings

The results are presented of a survey planned to assess the presence of high concern chemicals in sediments collected in a northern sector of the Adriatic sea neighboring the Venice lagoon. For the assessment, persistent marker chemicals were selected from the families of polycyclic aromatic hydrocarbons, polychlorobiphenyls, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), and chlorinated pesticides. Based on the chemical-specific concentrations and PCDD+PCDF profiles determined in the sediments analyzed, dumping zones appear to have existed approximately 5-6km away from lagoon shoreline. Contamination levels exceed the quality criteria established by the pertinent Italian national regulation at many sampling sites, eventually reflecting ("fingerprinting") industrial activities once performed in the industrial settlement of Porto Marghera within the Venice lagoon. In coastal samples, concentration levels appear to be lower than those determined at offshore sampling sites.     

Tracing the fate of PCBs in forest ecosystems

Forests were shown to play an important role in influencing atmospheric concentrations and transport of persistent organic pollutants (POPs) in the environment. World forests cover more than 4 billion hectares and contain up to 80% of the above ground organic carbon. Given the lipophilic nature of POPs, this suggests that forests can influence the environmental fate of POPs at a global scale. POP accumulation in forest canopies still presents points of concern given the complexity of these ecosystems. In particular, the role of ecological parameters such as LAI (leaf area index) and SLA (specific leaf area) and their dynamics during the growing season was not sufficiently investigated yet. This paper reviews, compares and interprets a unique case study in which air and leaf concentrations and deposition fluxes for selected polychlorinated biphenyls (PCBs) were measured in three different forest types exposed to the same air masses. In order to trace the air-leaf-soil path of these compounds, a dynamic model of POP accumulation into forest canopy was applied. The dynamics of the canopy biomass strongly affected the trend of leaf concentration with time. Growth dilution effect can prevent the more chlorinated compounds from reaching the partitioning equilibrium before litter fall, while the more volatile compounds can approach equilibrium in the range of few weeks. An amount of up to 60 ng of PCBs per square metre of ground surface was predicted to be stored in each of the selected forests at fully developed canopy. Dry gaseous deposition fluxes to forest canopy were estimated to reach a maximum value of about 0.5-1.5 ng m(-2) d(-1) during the spring period.     

The use of tree-rings and foliage as an archive of volcanogenic cation deposition

Tree cores (Pinus nigra ssp. laricio) and leaves (Castanea sativa) from the flanks of Mount Etna, Sicily were analysed by ICP-MS to investigate whether volcanogenic cations within plant material provide an archive of a volcano's temporal and spatial depositional influence. There is significant compositional variability both within and between trees, but no systematic dendrochemical correlation with periods of effusive, explosive or increased degassing activity. Dendrochemistry does not provide a record of persistent but fluctuating volcanic activity. Foliar levels of bioaccumulated cations correspond to modelled plume transport patterns, and map short-term volcanic fumigation. Around the flanks of the volcano foliar variation is greater for volatile cations (Cs, Cd, Pb) than for lithophilic cations (Ba, Sr), consistent with trace-metal supply from volcanic aerosol during quiescent periods.