Oxidation of phosphorus compounds by Fenton's reagent

In the present work a Fenton's treatment for the oxidation of a phosphorous compounds mixture, simulating a match manufacturing industry wastewater, were studied. Experimental tests were performed on three sample solutions at a phosphorus concentration of 250, 500 and 750 mg/l. In each solution an equal amount of sodium phosphite and sodium hypophosphite was dissolved. The investigation of pH, temperature and reagents ratio on the oxidation rate led to the individuation of the optimal process operating conditions. The results show that Fenton's reagent provides a powerful conversion to phosphate of the phosphorous solution. In particular at pH=3.5 and 20 degrees C a residual concentration of non oxidized phosphorus in compliance with the Italian regulation limits for industrial wastewater disposal. Tests performed on sample solution of 500 mg/l P and 750 mg/l P by adding hydrogen peroxide and bivalent iron in three sequential steps led to similar reaction efficiencies to tests carried out adding both Fenton's reagents in one step, but with a remarkably lower reagents consumption.     

Efficient hydroxycarbonylation of aryl iodides using recoverable and reusable carbon aerogels doped with palladium nanoparticles as catalyst

Electron-rich and electron-poor aryl iodides are converted, in high to excellent yields, into the corresponding carboxylic acids through a hydroxycarboxylation reaction catalyzed by a recoverable and reusable phosphine free palladium-carbon aerogel catalyst using lithium formate and acetic anhydride as an internal condensed source of carbon monoxide. The catalyst system can be reused several times without any appreciable loss of activity.     

Structural analysis of lignin in chestnut wood by pyrolysis-gas chromatography/mass spectrometry

The goal of the study was to determine the percentage of lignin in chestnut wood and to characterize structurally this polymer by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) according to a possible influence on ring shake defect. The sampling was performed in different sites of Lazio Region in Italy. Wood disks from trees with ring shake defect and without ring shake defect were selected and little amount of heartwood (1-2 g) sampled between 6th and 10th and between 11th and 15th annual growth ring were analyzed. The study allowed quantifying lignin content, which is in average 26% and syringyl/guaiacyl (S/G) ratio, which present an average value of 2.43. Belong the pyrolysis products of wood, the trees characterized by ring shake show a higher concentration of the phenol homosyringaldehyde respect to the healthy trees. There is not any evident difference in the products composition of pyrolysis in respect to trees’ age, especially the critical period of 12-14 years in which ring shake generally becomes more evident. The site of wood provenance is the higher factor of variability in the structure of lignin for many phenols.     

Experimental assessment of electrochemical processes in the remediation of atrazine contaminated soils

The electrochemical oxidation of an atrazine solution obtained from a flushing treatment of a contaminated soil was investigated. The influence of ethanol on atrazine oxidation was studied. Results show that the electrogenerated Fenton's reagent provides a complete degradation of atrazine and its main chlorinated by-products via N-dehalkylation and dechlorination. This process therefore presents an effective alternative to the chemical oxidation treatment which necessarily needs a further biological state.     

Polychlorinated androstanes from the burrowing sponge Cliona nigricans

Two new steroidal derivatives, named clionastatins A and B, have been isolated from the burrowing sponge Cliona nigricans. These molecules are tri-and tetrachlorinated androstane derivatives, respectively, and they represent the first polyhalogenated steroids found in a natural organism, either marine or terrestrial, and the first examples of halogenated androstanes in nature. Both clionastatins proved to be potently cytotoxic.     

Determination of arsenic by hollow-cathode emission spectrometry

The applicability of the hollow-cathode discharge source in the emission spectrometric determination of arsenic is described. Neutral and 10% nitric acid solutions, as well as solutions obtained by mineralization of biological materials, all containing 2.5 to 125 μg As cm^?3, were introduced into stainless steel cathodes, dried under i.r. radiation, and calcined in a muffle furnace; the loaded cathodes were then subjected to discharge. Acidic solutions were found to leach nickel from the steel of the cathode: this converted the analyte into thermally-stable nickel arsenide, thus minimizing losses. Matrix effects were small, and the r.s.d. was satisfactory (5–8%). The detection limit was 3 μg cm^?3.     

Photoelectron resonance capture ionization mass spectrometry: a soft ionization source for mass spectrometry of particle-phase organic compounds

Photoelectron resonance capture ionization (PERCI) is a soft and sensitive ionization method, based on the attachment of low-energy (<1 eV) photoelectrons to organic analyte molecules. PERCI has been developed in our laboratory for the real-time analysis of organic particles by mass spectrometry, and is employed here to monitor the heterogeneous reaction of ozone with oleic acid. Simplified identification of the reaction products is possible as a result of the soft nature of PERCI, giving predominantly the [M--H](-) ions. The major particle-phase products are identified as: 1-nonanal, nonanoic acid, 9-oxononanoic acid, and azelaic acid, consistent with proposed mechanisms. New insight into this well-studied heterogeneous reaction is gained as additional minor particle-phase products, consistent with the Criegee mechanism, are readily detected.     

Innovative methods for removing phosphorus from wastewaters

Wastewater containing a mixture of hypophosphites and phosphites was treated in order to assess the possibility of attaining high levels of phosphorus oxidation to phosphate. An initial series of tests based on chemical oxidation by means of Fenton's reagent demonstrated the feasibility of this process for solutions containing 250-750 mg/l of phosphorus. Removal yields of up to 98% were attained at pH 3.5 by using variable ratios of [H2O2]/[Fe2+]. The second series involved the electrolytic generation of Fenton's reagent at pH 2-2.5 through cathodic oxygen reduction. This demonstrated the possibility of obtaining quantitative yields for solutions containing 80-160 mg/l P with a constant [H2O2]/[Fe2+] ratio of 3.94. Economic comparison of the two processes showed that the operative cost of the electrochemical treatment is comparable to that of the chemical process.