Matilda Mali

Are conventional statistical techniques exhaustive for defining metal background concentrations in harbour sediments? A case study: The Coastal Area of Bari (Southeast Italy)

Sediment contamination by metals poses significant risks to coastal ecosystems and is considered to be problematic for dredging operations. The determination of the background values of metal and metalloid distribution based on site-specific variability is fundamental in assessing pollution levels in harbour sediments. The novelty of the present work consists of addressing the scope and limitation of analysing port sediments through the use of conventional statistical techniques (such as: linear regression analysis, construction of cumulative frequency curves and the iterative 2σ technique), that are commonly employed for assessing Regional Geochemical Background (RGB) values in coastal sediments. This study ascertained that although the tout court use of such techniques in determining the RGB values in harbour sediments seems appropriate (the chemical-physical parameters of port sediments fit well with statistical equations), it should nevertheless be avoided because it may be misleading and can mask key aspects of the study area that can only be revealed by further investigations, such as mineralogical and multivariate statistical analyses.

Resin-Immobilized Palladium Nanoparticle Catalysts for Organic Reactions in Aqueous Media: Morphological Aspects

An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)2 [AAEMA− = deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate as co-monomer, and ethylene glycol dimethacrylate as cross-linker. This material was used in water for the Suzuki-Miyaura cross-coupling of aryl bromides, and for the reduction of nitroarenes and quinolines using NaBH4 or H2, as reductants. TEM analyses showed that in all cases the pristine Pd(II) species were reduced in situ to Pd(0), which formed metal nanoparticles (NPs, the real active species). The dependence of their average size (2–10 nm) and morphology on different parameters (temperature, reducing agent, presence of a phase transfer agent) is discussed. TEM and micro-IR analyses showed that the polymeric support retained its porosity and stability for several catalytic cycles in all reactions and Pd NPs did not aggregate after reuse. The metal nanoparticle distribution throughout the polymer matrix after several recycles provided precious information about the catalytic mechanism, which was truly heterogeneous in the hydrogenation reactions and of the so-called “release and catch” type in the Suzuki coupling.

Iron(II) modified natural zeolites for hexavalent chromium removal from contaminated water

Abstract Three different types of Fe(II)-modified natural zeolites were tested as supports in continuous-flow columns for the treatment of Cr(VI) contaminated water. The natural zeolites chosen as support were commercially available Zeosand (80% clinoptilolite), ATZ (79% phillipsite/chabazite), and ZS-55RW (90% Chabazite). All the examined modified zeolites turned out active for hexavalent chromium abatement, lowering its concentration below the European regulation level, even at relatively high flow rates (40 mL/h, linear velocity 15 cm/h). Zeosand, having a broader pH range of stability, was found to be the best one in terms of both Fe(II) uptake (0.54 wt%) and Cr removal (90 mg Cr/Kg zeolite).

Influence of hydrodynamic features in the transport and fate of hazard contaminants within touristic ports. Case study: Torre a Mare (Italy)

The environmental quality of Torre a Mare port (Italy) was assessed evaluating on one side, the chemical concentration of nine metals and metalloids within bottom sediments and on the other one, by exploring the impact of hydrodynamic conditions in contaminant’s transport within the most polluted basins. The investigated port was selected as case study because it resulted much more polluted than it was expected based on the touristic port activities and related stressors loading on it. In order to determine the origin and fate of contaminants in the port basin, 2D numerical simulations were carried out by MIKE21 software. The hydrodynamic module (HD) based on a rectangular grid was initially used to characterize the flow field into two domains that cover the inner and offshore harbor area. Then, advection–dispersion (AD) and water quality (WQ) modules were coupled in order to simulate the simultaneous processes of transport and dispersion of hypothetical pollutant sources. The dissolved/suspended sediment particulates (DSS) were selected as contaminant tracers. The comparative analysis between simulation responses and the real metal contaminant distribution showed high agreement, suggesting that contaminants mainly come from outside port and tend to accumulate in the inner basin. In fact, hydrodynamic circulations cause inflowing streams toward the harbor entrance and the particular port morphology hampers the exit of fine sediments from the inner basin, enhancing thus the accumulation of sediment-associated contaminants within the port area. The study confirms that the quality of touristic port areas strongly depends on both pollution sources located within and outside the port domain and it is controlled mainly by the hydrodynamic-driven processes.

Combining chemometric tools for assessing hazard sources and factors acting simultaneously in contaminated areas. Case study: “Mar Piccolo” Taranto (South Italy)

Almost all marine coastal ecosystems possess complex structural and dynamic characteristics, which are influenced by anthropogenic causes and natural processes as well. Revealing the impact of sources and factors controlling the spatial distributions of contaminants within highly polluted areas is a fundamental propaedeutic step of their quality evaluation. Combination of different pattern recognition techniques, applied to one of the most polluted Mediterranean coastal basin, resulted in a more reliable hazard assessment. PCA/CA and factorial ANOVA were exploited as complementary techniques for apprehending the impact of multi-sources and multi-factors acting simultaneously and leading to similarities or differences in the spatial contamination pattern. The combination of PCA/CA and factorial ANOVA allowed, on one hand to determine the main processes and factors controlling the contamination trend within different layers and different basins, and, on the other hand, to ascertain possible synergistic effects. This approach showed the significance of a spatially representative overview given by the combination of PCA-CA/ANOVA in inferring the historical anthropogenic sources loading on the area.

Assessment and source identification of pollution risk for touristic ports: Heavy metals and polycyclic aromatic hydrocarbons in sediments of 4 marinas of the Apulia region (Italy)

The Apulia region in Italy has the longest Adriatic coastline; thus, maritime tourism is the driving force for its economic development. Pollution risk for four representative touristic ports of the region was assessed by determining the concentrations of 10 metals, 16 polycyclic aromatic hydrocarbons (PAHs) congeners, and the main nutrients. The cumulative mean Effects Range-Median quotient (mERMq) was used to assess the hazard degree, while the distribution patterns and content ratios of different PAH sediment concentrations were investigated to identify the pollution sources. Principal component analyses indicated an anomalous pollution trend for one of the small touristic ports assessed; this trend emerged from contamination by heavy metals and PAHs to a larger extent than expected, considering the main activity in this port, especially in its inner basin. The reason of this anomaly is thought to be the hydrodynamic and/or other stress factors.

Catalytic activities of heterogeneous catalysts obtained by copolymerization of metal-containing 2-(acetoacetoxy)ethyl methacrylate

Abstract Among the synthetic strategies commonly used for supporting a metal complex onto an organic polymer in order to obtain an heterogenous catalyst, a valid choice is to synthesize a metal containing monomer (MCM), which can subsequently be subjected to polymerization with suitable comonomers and crosslinkers, achieving a supported transition metal catalyst as a metal-containing polymer (MCP). In this context, during the last two decades, we explored the use of 2-(acetoacetoxy)ethyl methacrylate (HAAEMA) as a ligand to prepare several MCMs for the relevant MCPs. In this review we summarize and discuss our developments in the studies of the catalytic activity of these “hybrid” catalysts. These catalysts have demonstrated high efficiency and/or excellent selectivity in several kinds of chemical reactions and very often they could be recovered and reused in multiple cycles maintaining their activity and selectivity without suffering from appreciable metal leaching.

Catalytic activity and recyclability of polymer supported palladium or nickel nanoparticles in organic reactions in water

B is a clean, renewable and abundant resource that can be converted to bio-char, bio-oil and fuel gas through various thermochemical processes. Conversion of biomass for high value products is an important development direction for biomass utilization, which has attracted more attention. In this study, a new method of biomass pyrolysis with exogenous nitrogen introduced was proposed. The influence of NH3 on the property of bamboo pyrolysis process and products characteristics was investigated with variant approaches (e.g. elemental analysis, automatic adsorption equipment, X-ray photoelectron spectroscopy and CHI760 electrochemical workstation) and as well as the influence of KOH (as activator). The results showed that, the specific surface area, the content of nitrogen and nitrogen-containing functional groups of bio-char increased significantly with NH3 introduced in. On the other hand, with the addition of KOH, the yield of bio-char increased obviously and it increased gradually with increasing KOH amount, and the specific surface area increased dramatically to 1873.17 m2 g-1. The content of nitrogen in bio-char increased greatly with KOH introduced in, especially the content of pyridinic-N and pyrrolic/pyridone-N, while it decreased slightly with increasing KOH amount, but nitrogen content was still relative high (9.1-10.4 wt.%). The formation mechanism of nitrogen-containing functional groups was proposed. Besides, electrochemical analysis showed that the specific capacitance of bio-char electrodes increased with increasing KOH content, and the largest specific capacitance could reach to 187 F g-1 at 1 A g-1 with good cycling stability. Therefore, it could be concluded that biomass nitrogen-enriched pyrolysis was a promising method for more efficient utilization of biomass resources.A insoluble palladium catalyst (Pd-pol) was obtained by copolymerization of the metal containing monomer Pd(AAEMA)2 [AAEMA− = deprotonated form of 2-(acetoacetoxy)ethyl methacrylate] with ethyl methacrylate (co-monomer) and ethylene glycol dimethacrylate (cross-linker), followed by in situ reduction of Pd(II) to Pd(0), to give polymer stabilized metal nanoparticles. The good swellability in water exhibited by Pd-pol rendered it an ideal potential catalyst for reactions carried out in a green solvent, such as water, since the migration of the reagents to the active sites would not be hampered by the solid support. With the aim to develop innovative catalytic processes that enable chemical transformations to be performed under mild and sustainable conditions with high efficiency, we decided to evaluate the catalytic activity of Pd-pol for several important organic reactions using water as solvent. Pd-pol resulted highly active and selective in catalyzing (figure 1): the Suzuki-Miyaura coupling between aryl bromides or activated aryl chlorides and phenylboronic acid; the oxidation of benzyl alcohols to aldehydes; the reduction of quinolines and nitroarenes by H2 or NaBH4. Pd-pol was recyclable for several consecutive runs (for example, at least 12 times in the nitroarene reduction). TEM analyses carried out on the catalyst showed that the active species were supported palladium nanoparticles having a mean size of 4 nm, which did not aggregate with the recycles. Recently, due to their low cost, Ni catalysts have been employed in several organic reactions (mainly hydrogenations). In this context, we synthetized a Ni catalyst similar to Pd-pol, starting from Ni(AAEMA)2 and we employed it as active and recyclable, insoluble catalyst for the reduction of different nitroarenes to give the corresponding anilines, under sustainable conditions. All these results proved that the proposed Pd or Ni based composite materials are excellent hybrid structures as efficient and reusable catalysts.A amino acids are versatile structures readily available by a number of methods and are accessible using very few transformations from economical starting materials. They can be functionalized by many chemical functions and offer a wide range of possible transformations. Particularly, unsaturated α-amino acids give access to many synthetic applications in all fields of chemistry. Among them, metal catalyzed cross-coupling reactions and cross metathesis are commonly used to generate peptide modifications and cyclization. They are very interesting and useful tools for “Click” Chemistry in peptidomimetic drug design or covalent modification of proteins. They can also be incorporated in compounds as beta-turn inducer to promote secondary structures. Finally they can be used for the preparation of stapled peptides. Some such amino acids are commercially attainable in enantiomerically pure form. Here, we present a stereoselective approach to synthesize unsaturated α-amino acids in optically active form. As a starting amino acid synthon for the asymmetric synthesis of amino acids NiII square-planar complexes of Schiff ’s bases of propargylglycine with chiral auxiliary (S)-2-N-(N`-benzyl-prolyl)aminobenzophenone (BPB) (1) was taken. As a result effective methods of asymmetric synthesis for novel enantiomerically enriched derivatives of (S)-propargylglycine (S)-propargylglycine (ee > 80%) was developed.