Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: a new methodological approach

Introduction  

In this work, we propose an innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a methodological approach for the chemical characterisation of black crusts on stone monuments, associated with traditional micro-morphological (optical and scanning electron microscopy) and infrared spectroscopic techniques (FTIR).     

Ozone uptake by citrus trees exposed to a range of ozone concentrations

The Citrus genus includes a large number of species and varieties widely cultivated in the Central Valley of California and in many other countries having similar Mediterranean climates. In the summer, orchards in California experience high levels of tropospheric ozone, formed by reactions of volatile organic compounds (VOC) with oxides of nitrogen (NO_x). Citrus trees may improve air quality in the orchard environment by taking up ozone through stomatal and non-stomatal mechanisms, but they may ultimately be detrimental to regional air quality by emitting biogenic VOC (BVOC) that oxidize to form ozone and secondary organic aerosol downwind of the site of emission. BVOC also play a key role in removing ozone through gas-phase chemical reactions in the intercellular spaces of the leaves and in ambient air outside the plants. Ozone is known to oxidize leaf tissues after entering stomata, resulting in decreased carbon assimilation and crop yield. To characterize ozone deposition and BVOC emissions for lemon (Citrus limon), mandarin (Citrus reticulata), and orange (Citrus sinensis), we designed branch enclosures that allowed direct measurement of fluxes under different physiological conditions in a controlled greenhouse environment. Average ozone uptake was up to 11 nmol s^?1 m^?2 of leaf. At low concentrations of ozone (40 ppb), measured ozone deposition was higher than expected ozone deposition modeled on the basis of stomatal aperture and ozone concentration. Our results were in better agreement with modeled values when we included non-stomatal ozone loss by reaction with gas-phase BVOC emitted from the citrus plants. At high ozone concentrations (160 ppb), the measured ozone deposition was lower than modeled, and we speculate that this indicates ozone accumulation in the leaf mesophyll.     

Temporal trends of elements in Turin (Italy) atmospheric particulate matter from 1976 to 2001

The temporal trends of major, minor and trace elements in the total atmospheric particulate sampled in the urban area of Turin (Italy) were determined for the following years: 1976, 1986, 1996 and 2001. The wavelength dispersive X-ray fluorescence (WD-XRF) technique was adopted to determine the concentrations of Ba, Br, Ca, Cl, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, S, Ti and Zn. A smaller number of samples was also analysed by ICP atomic emission spectroscopy (ICP-AES) and the results were compared with those obtained by WD-XRF to confirm their validity. A clear seasonal pattern with higher concentrations of the aforementioned elements in the cold periods was observed. Moreover, a change in the chemical composition of atmospheric particulate matter was evidenced, particularly between the first (1976 and 1986) and the last (1996 and 2001) years. This change can be attributed both to the greater contribution of Pb and Br to atmospheric pollution in the past and, in recent years, to the higher level of pollutants associated with increased vehicular traffic and industrial activities. The application of chemometric techniques (Principal Component Analysis and Cluster Analysis) allowed us to speculate about the main emitting sources influencing the total atmospheric particulate in these years.     

End-of-Life Vehicles management: Italian material and energy recovery efficiency

Each European Member State must comply with Directive 2000/53/EC recycling and recovery targets by 2015, set to 85% and 95%, respectively. This paper reports a shredder campaign trial developed and performed in Italy at the beginning of 2008. It turns out to be the first assessment about the critical aspects belonging to the Italian End-of-Life Vehicles (ELVs) reverse supply chain involving 18 dismantling plants, a shredder plant and 630 ELV representatives of different categories of vehicles treated in Italy during 2006. This trial aims at improving the experimental knowledge related to ELVs added waste, pre-treatment, part reuse, recycling and final metal separation and car fluff disposal. Finally, the study also focuses on the calculation of the effective Italian ELV recycling rate, which results equal to 80.8%, and auto shredder residue (ASR) characterization. According to the results obtained in this work, ASR still contains up to 8% of metals and 40% of polymers that could be recovered. Moreover, physical-chemical analysis showed a Lower Heat Value of almost 20,000 kJ/kg and revealed the presence of pollutants such as heavy metals, mineral oils, PCBs and hydrocarbons.     

Indicators of waste management efficiency related to different territorial conditions

The amount of waste produced and the control of separate collection are crucial issues for the planning of a territorial Integrated Waste Management System, enabling the allocation of each sorted waste fraction to the proper treatment and recycling processes. The present study focuses on assessing indicators of different waste management systems in areas characterized by different territorial conditions. The investigated case study concerns the municipalities of Emilia Romagna (northern Italy), which present a rather uniform socioeconomic situation, but a variety of geographic, urban and waste management characteristics. A survey of waste generation and collection rates was carried out, and correlated with the different territorial conditions, classifying the municipalities according to altitude and population density. The best environmental performances, in terms of high separate collection rate, were found on average in rural areas in the plain, while the lowest waste generation was associated with rural hill towns.     

Treatment of exhaust fluorescent lamps to recover yttrium: experimental and process analyses

The paper deals with recovery of yttrium from fluorescent powder coming from dismantling of spent fluorescent tubes. Metals are leached by using different acids (nitric, hydrochloric and sulphuric) and ammonia in different leaching tests. These tests show that ammonia is not suitable to recover yttrium, whereas HNO(3) produces toxic vapours. A full factorial design is carried out with HCl and H(2)SO(4) to evaluate the influence of operating factors. HCl and H(2)SO(4) leaching systems give similar results in terms of yttrium extraction yield, but the last one allows to reduce calcium extraction with subsequent advantage during recovery of yttrium compounds in the downstream. The greatest extraction of yttrium is obtained by 20% w/v S/L ratio, 4N H(2)SO(4) concentration and 90°C. Yttrium and calcium yields are nearly 85% and 5%, respectively. The analysis of variance shows that acid concentration alone and interaction between acid and pulp density have a significant positive effect on yttrium solubilization for both HCl and H(2)SO(4) medium. Two models are empirically developed to estimate yttrium and calcium concentration during leaching. Precipitation tests demonstrate that at least the stoichiometric amount of oxalic acid is necessary to recover yttrium efficiently and a pure yttrium oxalate n-hydrate can be produced (99% grade). The process is economically feasible if other components of the fluorescent lamps (glass, ferrous and non-ferrous scraps) are recovered after the equipment dismantling and valorized, besides the cost that is usually paid to recycling companies for collection, treatment or final disposal of such fluorescent powders.     

Can a marine pest reduce the nutritional value of Mediterranean fish flesh?

Biological invasions are deemed as one of the most severe threats to biodiversity and can result in huge economic impacts on natural resources. Many studies have assessed structural changes caused by the introduction of nonindigenous species, but urgent questions remain to be answered about the complex indirect effects of invasive pests on marine biodiversity at the species and ecosystem level. Previous investigations focusing on the biological invasion by Caulerpa racemosa in the Mediterranean indicated that the lipophilic algal metabolite caulerpin accumulates in the tissues of the native edible white sea bream Diplodus sargus feeding on the exotic alga. The level of caulerpin in D. sargus has been thus used as an indicator of the trophic exposure of the fish to the seaweed and related with adverse effects on the fish health. In the present study, we show that the C. racemosa-based diet can also alter muscle fatty acids composition in the white sea bream by reducing the percentage of polyunsaturated fatty acids of the n-3 and n-6 series, such as eicosapentaenoic (C20:5), docosahexaenoic (C22:6) and arachidonic acids (C20:4). This represents both a real threat to the health of fish unable to biosynthesize these essential fatty acids and an impoverishment of an important source of essential fatty acids for human nutrition, which helps to prevent cardiovascular diseases, diabetes, hepatic steatosis, cancer and neurological disorders. On the whole, this work sheds light on an unexplored and critical aspect of biological invasions with implication on the health of both humans and the environment.     

Motility of cryopreserved spermatozoa for the ecotoxicological evaluation of aquatic environments

A new approach to environmental studies was investigated by the authors, who propose the use of cryopreserved biological systems in ecotoxicological bioassays. The feasibility of spermiotoxicity tests using cryopreserved semen of the sea bream Sparus aurata, with sperm motility parameters as the endpoint, was evaluated. Thawed sperm was incubated in environmental samples (sediment elutriate and dumpsite leachate) and in a reference toxicant (cadmium) at scaled concentrations. Motility was then evaluated by video-microscopy using both visual and computer-assisted analyses. Activation time, sperm motility and velocity and motility duration were assessed on thawing and at the end of the incubation time, and the difference with respect to the control was statistically evaluated. All the endpoints of the bioassay proved to have good sensitivity even at the highest dilutions of the tested matrices. Observed differences in the sensitivity thresholds of the endpoints were considered to be representative of different aspects of sperm physiology. Therefore the proposed bioassay is a promising starting point for the development of toxicity tests that are increasingly tailored to the needs of ecotoxicology and environmental quality evaluation strategies for aquatic environments.