A simple procedure to harmonize class boundaries of assessment systems at the pan-European scale

A procedure for a large scale harmonization of assessment systems is delineated. The data collected for the two E.U. co-funded projects STAR and AQEM have been used as a benchmark dataset against which a test dataset derived from Italian standard monitoring programs was compared. A central step in the procedure adopted is the calculation of Intercalibration Common Metrics (STAR_ICMs). For both the benchmark and test datasets, six metrics were calculated, normalized and averaged to obtain an ICM index. The median values obtained for this index within each of the High and Good status classes, as defined within the STAR/AQEM dataset, were compared to the classes defined by the National method applied in Italy before WFD approval. The process of harmonization involved the re-positioning of the boundaries between Italian method quality classes until no more differences were found with the values observed in the STAR/AQEM samples. The re-setting of the Italian assessment boundaries by a step-by-step procedure lead to comparable STAR_ICM index values in the two datasets. Within this example, small refinements of the boundaries between high/good and good/moderate status were sufficient to harmonize the Italian assessment quality classes to the benchmark classification. Once a benchmark dataset is agreed among different countries, the procedure outlined can be easily applied to compare and harmonize assessment systems within and outside Europe. The main scientific and practical advantages of the procedure are listed and commented, especially facing the next steps of the Water Framework Directive Intercalibration process.     

Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

Cartilage chondroprotection and repair with pulsed electromagnetic fields: I-ONE therapy

Articular cartilage is a complex tissue characterised by chondrocytes that are embedded within an organised dense extracellular matrix of collagen and proteoglycan. Under physiologic condition, articular metabolism is slow, but under pathological condition turnover can increase and the matrix undergoes faster mechanical failure and deterioration, resulting in cartilage degeneration. Moreover, modest damage of the articular cartilage, resulting from trauma or less invasive surgical procedure, produces an inflammatory reaction of the joint cartilage, which can cause irreversible degeneration through the increase in catabolic cytokines synthesis and the decrease in anabolic activity of chondrocytes. Pro-inflammatory cytokines increase the synthesis of matrix-degrading enzymes and limit the production of proteoglycans. It is known that physical stimuli modulate cartilage metabolism. In particular, pulsed electromagnetic fields (I-ONE therapy, Igea, Carpi, Italy) allow to treat homogenously the whole cartilage surface and thickness and the underlying subchondral bone. In vitro I-ONE therapy increases the binding between adenosine and A_2A adenosine receptor on human neutrophils cell membrane, on bovine chondrocytes and on fibroblast-like synoviocytes. It has been shown that drugs with A_2A adenosine receptor agonist activity prevent articular cartilage degeneration in animals. We hypothesised that the adenosine agonist effect of I-ONE therapy can also prevent cartilage degeneration. In a recent study, De Mattei et al. demonstrated how I-ONE therapy can strongly inhibit the release of PGE₂ in bovine synovial fibroblasts exerting an anti-apoptotic effect on cells. Ex vitro, in bovine full thickness articular cartilage explants, I-ONE therapy induces the largest increase in proteoglycan synthesis and in IGF-1 synthesis, when cartilage is exposed to specific parameters of pulsed electromagnetic fields. These effective parameters were subsequently used in in vivo experiments. The effect of I-ONE therapy was investigated on Dunkin Hartley osteoarthritic knee by Mankin score and by histomorphometric and densitometric analysis; I-ONE therapy prevented cartilage degeneration and subchondral bone sclerosis. Osteochondral grafts were performed in the knees of sheep; I-ONE therapy favoured osteochondral grafts integration and prevented cyst-like resorption area formation, which can compromise the stability of graft and the success of the technique. To support the in vitro results, biochemical analyses of the synovial fluid were also performed in this animal model. The amount of inflammatory catabolic cytokines (IL-1β and TNF-α) in the synovial fluid of I-ONE treated animals was significantly lower than in control animals. On the contrary, TGF-β1 was significantly higher in stimulated animals than it was in controls. These results demonstrate not only the capability of I-ONE therapy to control the inflammatory reaction but also its capability to favour cartilage anabolic activity. These results provide the rational to design clinical studies to demonstrate the possibility to transfer the treatment to humans. Two randomised, prospective, double-blind clinical studies (Level I), one conducted to patients treated by arthroscopy with condroabrasion and/or perforations at the knee and the other after anterior cruciate ligament reconstruction, demonstrated that biophysical stimulation with I-ONE therapy leads to complete patient’s recovery in a significantly shorter time (P < 0.005). Moreover, a significant number of treated patients made lower use of anti-inflammatory drugs than the patients in the placebo group. We did not observe negative side effects, patient’s compliance was good and treatment was well accepted. I-ONE therapy significantly reduces patients’ recovery time, joint swelling and has a chondroprotective effect over articular cartilage. I-ONE treatment is a new therapy for the joint preservation.     

Postconsumer polyethylene terephthalate (PET)/polyolefin blends through reactive processing

Increasing awareness of environmental and energy problems has promoted greater governmental interest in selected waste collection and consequently has attracted the interest of several research groups to the challenge of converting recovered plastics into useful materials. The reactive blending of postconsumer polyethylene terephthalate (PET) with different polyolefins (PO) was studied in attempts to obtain a new material with enhanced properties with respect to the starting materials. The success of the project depends mainly on the possibility of obtaining a compatibilized blend between two starting polymers that, from chemical and thermomechanical viewpoints, are very different. This was approached by employing polyolefins bearing functional groups capable of specific interaction or chemical reaction with PET end groups. Ternary blends of very low density polyethylene (VLDPE)/PET/functionalized polyolefin (FPO) in a weight composition of 70/20/10 and binary blends of FPO/PET in a weight composition of 90/10 were prepared and studied to obtain reinforced polyolefin thermoplastic materials. Reactive blending was achieved in a Brabender Plastograph with a mixing chamber of 30 or 50cm³, at 250°C, and 40rpm for 10min. Differential scanning calorimetry, scanning electron microscopy, and tensile tests were used to investigate the phase behavior, the efficiency of compatibilization, and the mechanical properties of the blends.     

A mild photochemical approach to the degradation of phenols from olive oil mill wastewater

Photooxidation of cathecol (1) is carried out in aqueous solution at lambda > 300 nm using different sensitizers: rose bengal (RB), 9,10-dicyanoanthracene (DCA), 2,4,6-triphenylpyrylium tetrafluoroborate (Pyryl). The highest degradation is observed in the UV/RB-sensitized reaction (66% after 15 h of irradiation), mineralization and formation of dimers are the final events. This procedure has been extended to tyrosol (2), caffeic acid (3), vanillic acid (4), 4-hydroxycinnamic acid (5) and 4-hydroxybenzoic acid (6) as well as to a mixture of all phenols. A reduced toxicity of the UV/RB-irradiated solutions of cathecol and tyrosol towards alga Ankistrodesmus braunii is also verified.     

Modeling the Landscape Drivers of Fire Recurrence in Sardinia (Italy)

Although recurrent fire events with very short return periods have the most dangerous effects on landscape degradation, only a few papers have explored the landscape ecological factors that drive the probability of fire recurrence. In this paper we apply a habitat suitability model for analyzing the spatial relationship between a selected set of landscape factors (mainly land use types) and fire recurrence in Sardinia (Italy) in the years 2005–2010. Our results point out that fire occurrence in already burned areas is lower than expected in natural and semi-natural land cover types, like forest and shrublands. To the contrary, like in all regions where human activity is the main source of fire ignitions, the probability of fire recurrence is higher at low altitudes and close to roads and to urban and agricultural land cover types, thus showing marked preference for those landscape factors denoting higher anthropogenic ignition risk.     

Characterisation of major component leaching and buffering capacity of RDF incineration and gasification bottom ash in relation to reuse or disposal scenarios

Thermal treatment of refuse derived fuel (RDF) in waste-to-energy (WtE) plants is considered a promising solution to reduce waste volumes for disposal, while improving material and energy recovery from waste. Incineration is commonly applied for the energetic valorisation of RDF, although RDF gasification has also gained acceptance in recent years. In this study we focused on the environmental properties of bottom ash (BA) from an RDF incineration (RDF-I, operating temperature 850-1000 °C) and a RDF gasification plant (RDF-G, operating temperature 1200-1400 °C), by evaluating the total composition, mineralogy, buffering capacity, leaching behaviour (both at the material’s own pH and as a function of pH) of both types of slag. In addition, buffering capacity results and pH-dependence leaching concentrations of major components obtained for both types of BA were analysed by geochemical modelling. Experimental results showed that the total content of major components for the two types of BA was fairly similar and possibly related to the characteristics of the RDF feedstock. However, significant differences in the contents of trace metals and salts were observed for the two BA samples as a result of the different operating conditions (i.e. temperature) adopted by the two RDF thermal treatment plants. Mineralogy analysis showed in fact that the RDF-I slag consisted of an assemblage of several crystalline phases while the RDF-G slag was mainly made up by amorphous glassy phases. The leached concentrations of major components (e.g. Ca, Si) at the natural pH of each type of slag did not reflect their total contents as a result of the partial solubility of the minerals in which these components were chemically bound. In addition, comparison of total contents with leached concentrations of minor elements (e.g. Pb, Cu) showed no obvious relationship for the two types of BA. According to the compliance leaching test results, the RDF-G BA would meet the limits of the Italian legislation for reuse and the European acceptance criteria for inert waste landfilling. RDF-I BA instead would meet the European acceptance criteria for non hazardous waste landfilling. A new geochemical modelling approach was followed in order to predict the leaching behaviour of major components and the pH buffering capacity of the two types of slags on the basis of independent mineralogical information obtained by XRD analysis and the bulk composition of the slag. It was found that the combined use of data regarding the mineralogical characterization and the buffering capacity of the slag material can provide an independent estimate of both the identity and the amount of minerals that contribute to the leaching process. This new modelling approach suggests that only a limited amount of the mineral phases that control the pH, buffering capacity and major component leaching from the solid samples is available for leaching, at least on the time scale of the applied standard leaching tests. As such, the presented approach can contribute to gain insights for the identification of the types and amounts of minerals that control the leaching properties and pH buffering capacity of solid residues such as RDF incineration and gasification bottom ash.