Daniele Goi

Wet oxidation of acetic acid catalyzed by doped ceria

Abstract A series of ceria-containing mixed oxides has been prepared and utilized as catalysts in the oxidation of acetic acid in water. The incorporation of even relatively small amounts of ZrO2 and MnOx or CuO into the fluorite lattice of CeO2 strongly enhances the redox properties of the material with a consequent promotion of the oxidation activity. The best results are obtained with the ternary mixed-oxides CeO2-ZrO2-CuO and CeO2-ZrO2-MnOx which benefit from a synergetic interaction between CeO2 (whose properties are already modified by the presence of Zr) and CuO or MnOx. Analysis of metal ion concentration in the effluents after reaction indicates also a high stability of the mixed-oxide catalysts under the conditions employed.

Salt-assisted thermal desorption of mercury from contaminated dredging sludge

In this study, we tested a new procedure for the decontamination of mercury-polluted dredging sludge (Marano-Grado Lagoon, northeastern Italy) based on cationic exchange associated with thermal desorption at a low temperature. Four mercury-polluted sludge slurries were treated using thermal desorption at 393 K for 2h. Three different salts, NaCl (sodium chloride), (CH(3))(4)NCl (tetramethylammonium chloride) and (C(4)H(9))(4)NCl (tetrabutylammonium chloride) were used as exchangers. The selected salts have a monovalent cationic part that progressively increases in molecular weight. The results show that the association of cationic exchange with thermal treatment leads to a significant improvement in the removal of mercury from the contaminated material at a low temperature compared to samples that were not treated with salt. The highest levels of decontamination were attained were obtained when the slurries, which had mercury pollution ranging from 20 to 200 ppm, were treated with a 15% solution of (C(4)H(9))(4)NCl. The efficiency of the removal at 393 K (from 24% up to 60%) depended on the nature of the sample. When the samples were treated at a similar temperature without the salt, no remediation of mercury was detected. Our results show that the thermal decontamination temperature can be significantly lowered by this remediation approach, which is the first example based on cationic exchange of the pollutant with an appropriate salt.

Land application of aerobic sewage sludge does not impair methane oxidation rates of soils.

The aim of this study was to measure and compare methane oxidation rates of arable and grassland soils that received 7.5t ha⁻¹ y⁻¹ of noncontaminated aerobically treated sewage sludge for ten years. Arable soils showed generally lower methane oxidation rates (from 6 to 15∗10⁻³ h⁻¹) than grassland soils (from 26 to 33∗10³ h⁻¹). Oxidation rate constants (k) of soils amended with sewage sludge were remarkably close to their respective untreated controls, but a soil, that had received a tenfold sewage sludge application (i.e. 75 t ha⁻¹ y⁻¹), showed a statistically significantly higher k-value. Laboratory addition of up to 1000 mg Pb g⁻¹ soil to this soil did not cause any significant change in methane oxidation, but caused a decrease from 13.9 to 10.9×10⁻³ h⁻¹ in the control soil. Addition of Zn was much more toxic than Pb, with a significant decrease at 300 μg g⁻¹ soil rate and an almost complete inhibition at 1500 μg g⁻¹ soil rate. Higher resistance was evident of sewage sludge treated soil in comparison to control soil, for both biomass C and CH₄ oxidation activity.

Catalytic Wet-oxidation of a Mixed Liquid Waste: COD and AOX Abatement

A series of catalytic wet oxidation (CWO) reactions, at temperatures of 430-500 K and in a batch bench-top pressure vessel were carried out utilizing a strong wastewater composed of landfill leachate and heavily organic halogen polluted industrial wastewater. A CeO2-SiO2 mixed oxide catalyst with large surface area to assure optimal oxidation performance was prepared. The catalytic process was examined during batch reactions controlling Chemical Oxygen Demand (COD) and Adsorbable Organic Halogen (AOX) parameters, resulting AOX abatement to achieve better effect. Color and pH were also controlled during batch tests. A simple first order-two stage reaction behavior was supposed and verified with the considered parameters. Finally an OUR test was carried out to evaluate biodegradability changes of wastewater as a result of the catalytic reaction.

Phototreatment of Water by Organic Photosensitizers and Comparison with Inorganic Semiconductors

Phototreatment of water is drawing the attention of many as a promising alternative to replace methods like chlorination, ozonization, and other oxidation processes, used in current disinfection methods limiting harmful side-products and by-products that can cause damage to the fauna and flora. Porphyrins, phthalocyanines, and other related organic dyes are well known for their use in photodynamic therapy (PDT). These photosensitizers cause cell death by generating reactive oxygen species (ROS) especially singlet oxygen in the presence of light. Such molecules are also being explored for photodynamically treating microbial infections, killing of unwanted pathogens in the environment, and oxidation of chemical pollutants. The process of photosensitisation (phototreatment) can be applied for obtaining clean, microbe-free water, thus exploiting the versatile properties of photosensitizers. This review collects the various attempts carried out for phototreatment of water using organic photosensitizers. For comparison, some reports of semiconductors (especially TiO2) used in photocatalytic treatment of water are also mentioned.

Potential of Ceria-Based Catalysts for the Oxidation of Landfill Leachate by Heterogeneous Fenton Process

In this study, ceria and ceria-zirconia solid solutions were tested as catalyst for the treatment of landfill leachate with a Fenton-like process. The catalysts considered in this work were pure ceria and ceria-zirconia solid solutions as well as iron-doped samples. All the catalysts were extensively characterized and applied in batch Fenton-like reactions by a close batch system, the COD (chemical oxygen demand) and TOC (total organic carbon) parameters were carried out before and after the treatments in order to assay oxidative abatement. Results show a measurable improvement of the TOC and COD abatement using ceria-based catalysts in Fenton-like process and the best result was achieved for iron-doped ceria-zirconia solid solution. Our outcomes point out that heterogeneous Fenton technique could be effectively used for the treatment of landfill leachate and it is worth to be the object of further investigations.

Rheology Measurements for Online Monitoring of Solids in Activated Sludge Reactors of Municipal Wastewater Treatment Plant

Rheological behaviour of recycled sludge from a secondary clarifier of a municipal wastewater treatment plant was studied by using the rate controlled coaxial cylinder viscometer Rotovisko-Haake 20, system M5-osc., measuring device NV. The tests (hysteresis cycles) were performed under continuous flow conditions and following an ad hoc measurement protocol. Sludge shear stress versus shear rate curves were fitted very satisfactorily by rheological models. An experimental equation correlating the solid concentration of sludge to relative viscosity and fitting satisfactorily flow curves at different Total Suspended Solids (TTS%) was obtained. Application of the empirical correlation should allow the monitoring of the proper functioning of a wastewater treatment plant measuring viscosity of sludge.

Biological evaluation of a Porphyrin-SPION nanoconjugate as an antimicrobial magnetic photosensitizer

The present work describes the use of a magnetic porphyin (5-(4-carboxy-phenyl)-10,15,20-triphenyl-21H, 23H-porphyrin TPP) nanoconjugate (SPION-TPP) for destroying pathogenic bacteria followed by the recovery of the magnetic photosensitizer. SPION-TPP was tested for its activity against two different gram-positive bacterial strains (Staphylococcus aureus and Steptoccoccus mutans). It is observed that SPION-TPP at a very low concentration of 0.5 μM is effective in destroying gram-positive bacteria (107–108 CFU ml-1) S. aureus with several orders reduction and few orders in S. mutans. The aim of this work is to combine photoactivity against microorganisms imparted by the photosensitizer with the possibility of recovering the nanoconstruct with magnets for disposal/reuse.