Behavior of TiO2 nanoparticles during incineration of solid paint waste: A lab-scale test

In order to assess the potential impacts posed by products containing engineered nanoparticles, it is essential to generate more data about the release of these particles from products’ life cycle. Although first studies were performed to investigate the release of nanoparticles from use phase, very few data are available on the potential release from recycling or disposal of nano-enhanced products.In this work, we investigated the behavior of TiO₂ nanoparticles from incineration of solid paint waste containing these particles. Solid paint debris with and without TiO₂ nanoparticles were treated in a lab scale incineration plant at 950 °C (combustion temperature) and in oxidizing atmosphere. The obtained ashes were also vitrified with additives and the release of Ti was finally evaluated by leaching test. From our incineration lab-scale experiment, we did not observe a release of TiO₂ nanoparticles into the atmosphere, and Ti was attached to the surface of obtained solid residues (i.e. ashes). The characterization of ashes showed that TiO₂ nanoparticles reacted during the incineration to give calcium titanate. Finally, a very low release of Ti was measured, less 1 mg/kg, during the leaching test of ashes vitrified with glass cullet and feldspathic inert. Our work suggests that TiO₂ nanoparticles added in paints may undergo to physicochemical transformation during the incineration, and that Ti found in ashes may be strongly immobilized in glass matrix. Since this conclusion is based on lab-scale experiment, further research is required to identify which nanoparticles will be emitted to the environment from a real-word-incineration system of household hazardous waste.     

Synthesis and Characterization of Lactic Acid Oligomers: Evaluation of Performance as Poly(Lactic Acid) Plasticizers

The use of fully bio-based and biodegradable materials for massive applications, such as food packaging, is an emerging tendency in polymer research. But the formulations proposed in this way should preserve or even increase the functional properties of conventional polymers, such as transparency, homogeneity, mechanical properties and low migration of their components to foodstuff. This is not always trivial, in particular when brittle biopolymers, such as poly(lactic acid) (PLA), are considered. In this work the formulation of innovative materials based on PLA modified with highly compatible plasticizers, i.e. oligomers of lactic acid (OLAs) is proposed. Three different synthesis conditions for OLAs were tested and the resulting additives were further blended with commercial PLA obtaining transparent and ductile materials, able for films manufacturing. These materials were tested in their structural, thermal and tensile properties and the best formulation among the three materials was selected. OLA with molar mass (M_n) around 1,000 Da is proposed as an innovative and fully compatible and biodegradable plasticizer for PLA, able to replace conventional plasticizers (phthalates, adipates or citrates) currently used for films manufacturing in food packaging applications.     

Adaptive cluster double sampling with post stratification with application to an epiphytic lichen community

The implementation of an adaptive cluster sampling design often becomes logistically challenging because variation in the final sampling effort introduces uncertainty in survey planning. To overcome this drawback, an inexpensive and easy to measure auxiliary variable could be used in a two-phase survey strategy, called adaptive cluster double sampling (Félix-Medina and Thompson in Biometrika 91:877–891, 2004). In this paper, a two-phase sampling strategy is proposed which combines the idea of adaptive cluster double sampling with the principle of post-stratification. In the first-phase an adaptive cluster sample is selected by means of an inexpensive auxiliary variable. Networks from the first phase sampling are then post-stratified according to their size. In the second-phase, the network structure is used to select a subsample of units by means of stratified random sampling. The proposed sampling strategy employs stratification without requiring an a priori delineation of the strata. Indeed, the strata sizes are estimated in the course of the two-phase sampling process. Therefore, it is suitable for situations where stratification is suspected to be efficient but strata cannot be easily delineated in advance. In this framework, a new type of estimator for the population mean which mimics the stratified sampling mean estimator and an estimator of the sampling variance are proposed. The results of a simulation study confirm, as expected, that the use of post-stratification leads to gain in precision for the estimator. The proposed sampling strategy is applied for targeting an epiphytic lichen community Lobarion pulmonariae in a forest area of the Northern Apennines (N-Italy), characterized by several species of conservation concern.     

Distribution of Cd and As in organs and tissues of four marine mammal species stranded along the Italian coasts

Concentrations of Cd and As were determined in organs and tissues (muscle, heart, kidney, lung and liver) of four cetacean species (Stenella coeruleoalba, Truncatus truncatus, Grampus griseus and Ziphius cavirostris) stranded along the Italian coasts during the period 2000-2009. Significant differences were found between Cd concentrations in the different analysed tissues. Particularly, the kidney shows the highest concentrations of Cd in all analysed specimens, followed by the liver. No systematic or statistically significant difference in As concentrations was found in the analysed tissues. Considerable differences of Cd and As values in samples from different geographical areas (Sicily Channel, Adriatic Sea and Tyrrhenian Sea) were found, with the highest values measured in samples from the Sicily Channel. This basically suggests that anthropogenic and natural sources significantly affect Cd and As content in cetaceans.     

TG, FT-IR and NMR characterization of n-C16H34 contaminated alumina and silica after mechanochemical treatment

This paper deals with the application of mechanochemistry to model systems composed of alumina or silica artificially contaminated with n-C16H34. The mechanochemical treatment was carried out by means of a ring mill for times ranging from 10 to 40h. Thermogravimetry and infrared and nuclear magnetic resonance spectroscopies were used for the characterization of the mechanochemical products. The results have indicated that, in the case of alumina, almost all the contaminant n-C16H34 undergoes a complex oxidative reaction path whose end products are strongly held on the surface. These end products are most likely made of crosslinked, partially oxidized hydrocarbon chains bond to the solid surface via COO(-) groups. In the case of silica, the hydrocarbon undergoes a different, equally complex reaction path, but to a lower extent. In this case the end products are most probably carbonylic compounds and graphitic carbon. Then, for both solid matrices, the mechanochemical treatment promotes significant modification of the chemical nature of the polluting hydrocarbon with end products much more difficult to remove from the surface. As the systems studied are models of sites contaminated by aliphatic hydrocarbon, the results are worthy of consideration in relation to the mobility of the contaminants in the environment.     

Environmental and biological monitoring of iridium in the city of Rome

The use of iridium in the latest catalytic converters to further reduce nitrogen oxide emission in the exhaust of lean-burn engines could result in increased atmospheric levels of this element in high-density vehicle traffic areas. The objective of this study is to assess environmental Ir pollution and its urinary levels in workers and an urban control group. Environmental monitoring inside a tram consisted in air samplings of total suspended particles (TSP), PM10 and PM2.5 carried out during November 2005. Urinary Ir levels were evaluated in 64 municipal tram drivers and in 58 administrative employees as controls. Quantification of Ir in air samples and urine was performed by means of Sector Field Inductively Coupled Plasma Mass Spectrometry. Means+/-standard deviation of Ir levels in TSP, in PM10 and PM2.5 fractions were 1.43+/-1.66, 0.44+/-0.27 and 0.36+/-0.19 pg m(-3), respectively. No statistically significant differences were observed among urinary Ir values in the exposed subjects and control group. The Ir levels in Rome air are still sufficiently low, even if the increased use of new Ir-based catalysts could be of some concern in the near future. The results of our study are of interest as they are a first attempt to explore airborne levels and urinary concentrations of Ir in an urban context at medium-high density of vehicle traffic. Particular attention should be given to the fact that Ir was found in the finest dust particles as the effects of fine particles containing Ir have not yet been studied.     

Evaluation of the impact on entomocoenosis of active agents allowed in organic olive farming against Bactrocera oleae (Gmelin, 1790)

Several attempts for evaluating environmental impact of active agents allowed in organic olive farming against Bactrocera oleae have been made, but very few studies were performed contemporaneously on more than one of them. Insects were chosen as indicators because they are known to react very quickly to environmental perturbations, mainly at the community level. In fact, the coenosis is the functional unit interacting with biotic and abiotic environmental parameters. Seven taxa, known for their sensitivity to habitat alterations, were sampled and grouped in functional groups: predators and parasitoids, phytophagouses and pollinators. The coenotic balance between these two functional groups was analyzed. The study was carried out in an organic olive orchard in the municipality of Terranova da Sibari, Cosenza, Southern Italy. The tested active agents (Azadirachtin, Rotenone, Copper Oxychloride) were sprayed twice (end of September and middle October). During the treatments the population dynamics of all the taxa were knocked-down. No one tested compound seems to be harmless to the entomocoenosis, particularly on phytophagouses and pollinators. In truly organic farming it is necessary to provide natural refuge areas to beneficial insects (i.e. pest antagonists) in which no active agents are sprayed and alternative preys could be found.     

Environmental release and mass flux partitioning of PCDD/Fs during normal and transient operation of full scale waste to energy plants

The paper reports on global release and mass partitioning in the flux of residues of PCDD/Fs, evaluated with dedicated field campaigns at a municipal solid waste incineration plant during normal and transient operation. Results are compared with those obtained in other installations equipped with furnaces, energy recovery options and flue gas treatment technologies representative of most of the European incineration plants currently in operation. Levels of the pollutants of interest were determined in all the solid, liquid and gaseous residues produced by every single facility, and the results analysed in terms of the effects arising from the fed waste and the configuration of the plant. PCDD/Fs total release between 1.5 and 45 microg I-TEQ per ton of burned waste was evaluated, with lower values resulting from the adoption of catalytic conversion process for flue gas treatment. Most of the mass flux emitted is associated with solid residues deriving from activated carbon PCCD/F dry removal options, with significant contributions also from fly ash produced by particulate removal devices located immediately downstream the boiler and from scrubber blowdowns treatment sludge. During transient operating conditions the dioxin total release may increase by 50% with comparison to steady-state functioning.