Ilaria Di Somma

Photodegradation of naproxen and its photoproducts in aqueous solution at 254 nm: a kinetic investigation.

The kinetics of photodegradation of the non steroidal anti-inflammatory drug naproxen (+)-S-2-(6-methoxynaphthalen-2-yl)propanoic acid, an emerging organic pollutant, was studied in aqueous solutions under deaerated and aerated conditions. The photolysis experiments were carried out under monochromatic irradiation (λ = 254 nm) at pH = 7.0 and T = 25 °C. Simplified reaction schemes of photodegradation of naproxen are proposed in absence and in presence of oxygen respectively. The schemes take into account the photolysis of naproxen and its photoproducts and the reactions of the measured species with oxygen dissolved in the liquid bulk. According to these schemes, two kinetic models were developed which correlate the experimental data, for runs performed in absence and in presence of oxygen, with a fair accuracy and allowed to estimate the best values for the unknown kinetic parameters. The calculated quantum yield of direct photolysis of naproxen under deaerated media is in good agreement with the one previously reported. Under aerated conditions, the generation of singlet oxygen has also been taken into account. The obtained results, under the adopted conditions, indicated a marked influence of dissolved oxygen on the photodegradation rates of naproxen and the relative distribution of the major reaction intermediates.

Kinetic investigation of Cu(II) ions photoreduction in presence of titanium dioxide and formic acid.

The photoreduction of Cu(II) in presence of an organic species as sacrificial agent has been investigated by many research groups but some controversial results are reported in literature. In this work, the photoreduction process of Cu(II) in presence of formic acid is investigated aiming at clarifying the reaction mechanism and assess the reaction kinetics. The effect of operating conditions such as TiO(2) load, initial concentration of sacrificial agent, pH and ionic strength was studied. The results of the work are: (1) the system reactivity does not depend neither on pH (in the range 2.0-3.5) nor on ionic strength of the solution; (2) formic acid is adsorbed on TiO(2) surface; (3) the nature of anionic species can influence the Cu(II) photoreduction (e.g. the addition of sulphate or phosphates reduces the reaction rates); and (4) FA can be completely mineralized during this photoxidation process; for example, this is observed for a TiO(2) load of 0.1g/L after a reaction time of about 240 min. A simplified kinetic model is developed to describe the behavior of the system and validated by analysing the data collected during the experimental work.

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable. Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10(-5) mol L(-1), in aqueous solutions through Fe(III)/O(2) homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O(2) homogeneous photocatalysis is less expensive than using H(2)O(2) due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH=3.0 and initial Fe(III) concentration equal to 1.5 · 10(-4) mol L(-1) although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism. The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10(-5)-5.2 · 10(-4) mol L(-1).

Kinetic and chemical characterization of thermal decomposition of dicumylperoxide in cumene

Dicumylperoxide (DCP) is one of the most used peroxides in the polymer industry. It has been reported that its thermal decomposition can result in runaway phenomena and thermal explosions with significant economic losses and injuries to people. In the present paper thermal behaviour of dicumylperoxide in cumene was investigated over the temperature range of 393-433 K under aerated and de-aerated conditions. The results indicated that when oxygen was present, the decomposition rate did not follow a simple pseudo-first order kinetic as previously reported in literature. A satisfactory fit of the experimental data was, in this case, achieved by means of kinetic expression derived under the assumption of an autocatalytic scheme of reaction. The reaction rate was, on the contrary, correctly described by a pseudo-first order kinetic in absence of oxygen. Under both aerated and de-aerated conditions, chemical analysis showed that the decomposition mainly resulted in the formation of acetophenone and dimethylphenylcarbinol with minor occurrence of 2,3-dimethyl-2,3-diphenylbutane. The formation of methane and ethane was also invariably observed while the appearance of cumylhydroperoxide as a reaction intermediate was detected under only aerated conditions. Therefore, two reaction schemes were proposed to explain system behaviour in the presence of oxygen and after its purging.

Fe(III)-photocatalytic partial oxidation of benzyl alcohol to benzaldehyde under UV-solar simulated radiation

A great deal of interest is recorded among researchers in the identification of new catalytic systems that make possible the selective oxidation of organic species in the presence of non-toxic solvents, primarily water, through the use of inexpensive catalysts. The possibility to selectively oxidize benzyl alcohol to benzaldehyde is studied in the present work by using ferric ions as homogeneous catalysts and oxygen as an oxidant under UV-solar simulated radiation. Due to the possibility that Fe(III) aquo-complex photolysis could generate undesired reactive OH radicals with the consequent occurrence of side reactions, most of the runs are carried out at pH = 0.5 at which these events have a reduced incidence. The results indicate that benzyl alcohol can be partially converted into benzaldehyde with yield and selectivity values higher than 40% and 80% respectively for the conditions adopted, with a minor occurrence of benzoic acid formation. Reaction schemes to account for the experimental observations are provided.

A procedure for the assessment of the toxicity of intermediates and products formed during the accidental thermal decomposition of a chemical species

The knowledge of the substances which form when a molecule undergoes chemical reactions under unusual conditions is required by European legislation to evaluate the risks associated with an industrial chemical process. A thermal decomposition is often the result of a loss of control of the process which leads to the formation of many substances in some cases not easily predictable. The evaluation of the change of an overall toxicity passing from the parent compound to the mixture of its thermal decomposition products has been already proposed as a practical approach to this problem when preliminary indications about the temperature range in which the molecule decomposes are available. A new procedure is proposed in this work for the obtainment of the mixtures of thermal decomposition products also when there is no previous information about the thermal behaviour of investigated molecules. A scanning calorimetric run that is aimed to identify the onset temperature of the decomposition process is coupled to an isoperibolic one in order to obtain and collect the products. An algal strain is adopted for toxicological assessments of chemical compounds and mixtures. An extension of toxicological investigations to human cells is also attempted.

A Kinetic Investigation on the Ozonation of Glycerol and its Oxygenated Derivatives

The ozonation of glycerol and its main oxygenated derivatives is studied aiming at evaluating the possibility to convert them into valuable products. The direct ozonation of glycerol results into a mixture of its oxygenated derivatives. In some cases the use of ozone to convert them into valuable products proceeds with good selectivity. A kinetic study to estimate the kinetic constants of ozone attack to the main glycerol oxygenated intermediates is carried out. The data found are in keeping with the few values found in the literature for alcoholic groups by ozone.

Removal of Copper, Iron and Zinc from Soil Washing Effluents Containing Ethylenediaminedisuccinic Acid as Chelating Agent Through Sunlight Driven Nano-TiO 2 -Based Photocatalytic Processes

The aim of the present study is the application of integrated solar nano-TiO2 based photocatalytic processes for the removal of copper, iron, zinc and (S,S)-ethylenediamine-N,N′-disuccinic acid (EDDS), used as chelating agent, from soil washing effluents produced by the remediation of samples of potentially polluted soils taken in the “Land of Fires” (Italy). Removal efficiencies of 93.5% (copper), 99.6% (iron), 99.4% (zinc), 97.2% (EDDS) and 80.7% (TOC) were reached through sunlight driven photocatalytic treatments carried out in parabolic trough collectors located in Naples (Italy). The removal degrees were achieved for an incident UVA solar energy per unit volume (Q j,n ) of 580 kJ L−1, estimated by taking into account both the effective irradiated surface area of the photoreactor (9.79 × 10−2 m2) and the local solar irradiances collected during the experiments. The combined nano-TiO2-photocatalytic processes applied were shown to sufficiently decontaminate the soil washing effluents to permit the recycling in the soil washing treatment or discharging to public sewers. The study suggests that the two-step solar photocatalytic process investigated can be really adopted as a useful solution for the decontamination of soil washing streams from some heavy metals and chelating organic agents.