Lignin/Poly(ε-Caprolactone) Blends with Tuneable Mechanical Properties Prepared by High Energy Ball-Milling

Polymer blends between lignin, a natural, widely available, no-cost material, and Poly(ε-caprolactone) (PCL), a biodegradable polymer, have been prepared using the ‘clean’, friendly to the environment, technique of the High Energy Ball Milling (HEBM). Two kinds of lignin have been used, Straw lignin, obtained through the Steam Explosion process (SE lignin), and/or Lignosulphonated one (LS lignin). The tensile mechanical tests have shown that, at certain specific compositions, the blends, in particular those with both SE and LS lignin, have good mechanical properties. In particular, by varying the blend composition it is possible to obtain materials with tuneable properties, therefore useful for different applications. Dynamic-Mechanical-Thermal Analysis (DMTA) reveals substantial immiscibility of the blends. Experiments of UV irradiation show that lignin acts as an UV stabilizer for PCL. The effect is higher with SE lignin, likely due to its low molecular weight, which allows the short lignin chains to diffuse more easily within the amorphous regions of PCL.     

Modelling the biphasic sorption of simazine,imidacloprid, and boscalid in water/soil systems

The sorption kinetics of simazine (6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine), imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine), and boscalid (2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide), three pesticides of wide use in agriculture, was determined in five different water/soil systems over a time interval from the initial few seconds to about 1 month. In all the experiments, sorption kinetics showed a biphasic pattern characterized by an initial, relatively short phase with a high sorption rate and a later phase with much a lower sorption rate. Initial sorption capacity increased with soil organic carbon content and with sorbate hydrophobicity. We postulate that the first phase of the process involves a fast second-order sorption reaction on superficial sites of soil particles, whereas the second phase depends on diffusion-controlled migration to internal binding sites. A kinetic equation based on this hybrid model accurately fitted all data sets. Less satisfactory results were obtained employing the pseudo-first order, pseudo-second order, Elovich, two site non-equilibrium, or Weber-Morris equation. The superior performance of the hybrid model for describing boscalid sorption probably reflects the high hydrophobic character and consequent low diffusion rates of this compound. The accuracy of modelling was in any case strongly dependent on the time interval considered.     

Toxic effects of four sulphonylureas herbicides on soil microbial biomass

The effect of four triazinyl-sulfonylurea herbicides (cinosulfuron, prosulfuron, thifensulfuron methyl, triasulfuron) on soil microbial biomass, soil respiration, metabolic activity, metabolic quotient, and some enzymatic activities (acid and alkaline phosphatase, β-glucosidase, arylsulphatase, and fluorescein diacetate hydrolysis) were monitored under controlled conditions over 30 days. The herbicides were applied at the normal field dose (FD) and at ten-fold (10 FD) the field dose, in order to mimic a long term toxic effect. The measured soil microbial parameters showed that the FD had slight effects on soil microflora, while at 10 FD the tested herbicides exerted a stronger detrimental effect on soil microbial biomass and its biochemical activities.     

Assessment of susceptibility of olive cultivars to the Bactrocera oleae (Gmelin, 1790) and Camarosporium dalmaticum (Thüm.) Zachos & Tzav.-Klon. attacks in Calabria (Southern Italy)

Within the framework of research concerning the application of techniques alternative to chemical pesticides for control of parasites, the C.R.A. Experimental Institute for Olive Growing for many years has been performing a large investigation in order to detect sources of genetic resistance in olive germplasm. In the present study we observed the behavior related to the olive fly (Bactrocera oleae) infestation and Camarosporium dalmaticum infection of ten olive cultivars farmed under the same agronomic and climatic conditions in Calabria, Southern Italy. The sampling and the data collecting were carried out in three different ripening times.The drupe amount of oleuropein and cyanidine was detected by laboratory analyses in order to verify a possible correlation between these molecules and the level of infestation/infection of the above-mentioned parasites. The obtained data were submitted to analysis of variance. In relation to the fungal infection the results displayed that cvs Tonda nera dolce showed the lowest susceptibility, while the cv Giarraffa turned out to be the most susceptible. The less susceptible cultivars to the phytophagous were Tonda nera dolce and Bhardi Tirana. Since the less susceptible cultivar to olive fly attacks are the same observed in relation to the susceptibility to olive fruit rot, it is suggested a relation between the olive fly infestation and the fungal infection. It suggests the utility to achieve these results both to transfer directly to the farmers' world and to emphasize ecosystem health and biodiversity conservation.     

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.     

Press-extrusion pretreatment of the organic fraction of municipal solid waste for enhanced methane production

Anaerobic digestion (AD) is a well-established process for the treatment of a wide variety of solid organic substrates, including the organic fraction of municipal solid waste (OFMSW). At industrial scale, the mechanical pretreatment is a fundamental step to reduce OFMSW particle size and to promote the hydrolysis within the subsequent AD process. Among the mechanical pretreatment technologies, press-extrusion has recently raised great interest for its possible application to either enhance the organic load to the digester or improve the overall process stability and methane yields. Aim of this study was in assessing the potential of the press-extrusion pretreatment to improve the performance of OFMSW anaerobic degradation. Batch tests were set up according to a full factorial design of experiments to assess the significance of the main operating parameters. The statistical analysis of results addressed further tests, carried out under semi-continuous feeding mode, to better discuss the possible application of press-extrusion for the greatest valorization of OFMSW under anaerobic conditions.

     

Ozone oxidation and aerobic biodegradation with spent mushroom compost for detoxification and benzo(a)pyrene removal from contaminated soil

The combination of ozonation and spent mushroom compost (SMC)-mediated aerobic biological treatment was investigated in the removal of benzo(a)pyrene from contaminated soil. The performances of the process alone and combined were evaluated in terms of benzo(a)pyrene removal efficiency, mineralization efficiency (as total organic carbon removal), and soil residual toxicity (phytotoxicity to Lepidium Sativum and toxicity to Vibrio fischeri). In spite of the removal efficiency (35%) obtained by SMC-mediated biological process as a stand-alone treatment, the combined process showed a benzo(a)pyrene concentration reduction higher than 75%; the best removal (82%) was observed after 10 min pre-ozonation treatment. In particular, ozonation improved the biodegradability of the contaminant, as confirmed by the increase of CO(2) production (close to 70% compared to the control), mineralization (greater than 60%) and bacterial density (which increased by two orders of magnitude). Moreover, according to phytotoxicity tests on L. Sativum, the aerobic biological process of pre-ozonated soil decreased toxicity. According to the results achieved in the present study, ozonation pre-treatment showed an high potential to overcome the limitation of bioremediation of recalcitrant compound, but it should be carefully operated in order to maximize PAH removal efficiency as well as to minimize soil residual toxicity which can result from the formation of the oxidation intermediates.