Danilo Spasiano

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.

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).

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.

Removal of benzoylecgonine from water matrices through UV254/H2O2 process: Reaction kinetic modeling, ecotoxicity and genotoxicity assessment.

Benzoylecgonine (BE), the main cocaine metabolite, has been detected in numerous surface water and treatment plants effluents in Europe and there is urgent need for effective treatment methods. In this study, the removal of BE by the UV254/H2O2 process from different water matrices was investigated. By means of competition kinetics method, the kinetic constant of reaction between BE and the photogenerated hydroxyl radicals (OH) was estimated resulting in kOH/BE=5.13×10(9)M(-1)s(-1). By-products and water matrices scavengers effects were estimated by numerical modeling of the reaction kinetics for the UV254/H2O2 process and validated in an innovative microcapillary film (MCF) array photoreactor and in a conventional batch photoreactor. The ecotoxicity of the water before and after treatment was evaluated with four organisms Raphidocelis subcapitata, Daphnia magna, Caenorhabditis elegans, and Vicia faba. The results provided evidence that BE and its transformation by-products do not have significant adverse effects on R. subcapitata, while D. magna underwent an increase of lipid droplets. C. elegans was the most sensitive to BE and its by-products. Furthermore, a genotoxicity assay, using V. faba, showed cytogenic damages during the cell mitosis of primary roots.

Treatments of asbestos containing wastes

Since the second half of the twentieth century, many studies have indicated inhalation of asbestos fibers as the main cause of deadly diseases including fibrosis and cancer. Consequently, since the beginning of the 80s, many countries started banning production and use of asbestos containing products (ACP), although still present in private and public buildings. Due to some extraordinary catastrophic events and/or the aging of these products, peoples health and environmental risk associated with the inhalation of asbestos fibers keeps being high even in those countries where it was banned. For these reasons, many communities are developing plans for an environmental and sanitary safe asbestos removal and management. Asbestos containing wastes (ACW) are usually disposed in controlled landfills, but this practice does not definitively eliminate the problems related with asbestos fiber release and conflicts with the ideas of sustainable land use, recycling, and closing material cycles. Consequently, many scientific papers and patents proposed physical, chemical, and biological treatments aimed to the detoxification of ACW (or the reduction of their health effects) and looking for the adoption of technologies, which allow the reuse of the end-products. By including recent relevant bibliography, this report summarizes the status of the most important and innovative treatments of ACW, providing main operating parameters, advantages, and disadvantages.

Ethylenediamine-N,N′-Disuccinic Acid (EDDS)—Enhanced Flushing Optimization for Contaminated Agricultural Soil Remediation and Assessment of Prospective Cu and Zn Transport

This paper presents the results of an experimental study aimed at investigating the effect of operative parameters on the efficiency of a soil flushing process, conducted on real contaminated soil containing high amounts of Cu and Zn. Soil flushing tests were carried out with Ethylenediamine-N,N′-disuccinic acid (EDDS) as a flushing agent due to its high biodegradability and environmentally friendly characteristics. Process parameters such as Empty-Bed Contact Time (EBCT) and EDDS solution molarity were varied from 21–33 h and from 0.36–3.6 mM, respectively. Effects on the mobility of cations such as Fe and Mn were also investigated. Results showed that very high performances can be obtained at [EDDS] = 3.6 mM and EBCT = 33 h. In these conditions, in fact, the amount of removed Cu was 53%, and the amount of removed Zn was 46%. Metal distribution at different depths from the top surface revealed that Cu has higher mobility than Zn. The process results were strongly dependent on the exchange of metals due to the different stability constants of the EDDS complexes. Finally, results from a comparative study showed that soil washing treatment reached the same removal efficiency of the flushing process in a shorter time but required a larger amount of the EDDS solution.

Photocatalytic Oxidation of Organic Micro-Pollutants: Pilot Plant Investigation and Mechanistic Aspects of the Degradation Reaction

An innovative pilot plant based on UVB and TiO2 (Anatase) allowed for photocatalytic degradation of organic micro-pollutants. The catalyst was immobilized onto a channel through which the solution containing a target molecule (methylene blue, MB) was re-circulated. Due to the cationic nature of the MB substrate, the adsorption reaction onto the catalyst surface provided a significant contribution to the overall degradation mechanism due to the negatively charged surface at neutral pH (TiO2 pHzpc = 6.8). The influence of the initial MB concentration was investigated in the range 0.3–2.0 mg L−1 with the Langmuir–Hinshelwood (LH) model showing good data correlations at concentrations up to 0.7 mg L−1, whereas at higher concentrations a pure zero-order (catalytic) kinetic trend was observed. Flow rate of the re-circulating solution sensibly influenced kinetics after the larger volumes of liquid exposed to UVB/TiO2 and to the better oxygen saturation in the liquid phase. UV−vis and HPLC-MS/MS experimental determinations allowed for identification of MB residual concentration and by-products.

Kinetic characterization of the photosynthetic reaction centres in microalgae by means of fluorescence methodology

The kinetic characterization of the photosynthetic activity in autotrophic microalgae plays a key role in the design of optimized photobioreactors. This paper presents a procedure to assess kinetic parameters of a three-state photosynthetic reaction centres model. Four kinetic parameters of the model were assessed by processing the time-series measurements of pulse-amplitude modulation fluorimetry. The kinetic parameters were assessed for several microalgal strains (Stichococcus bacillaris, Scenedesmus vacuolatus, Chlamydomonas reinhardtii, Chlorella vulgaris) growth in vertical and inclined bubble columns and irradiated by white-light or red/blue light. The procedure was successfully applied to the investigated strains. The assessed parameters allow identifying the irradiance range under which: the photochemical process is controlled by the photons capture; the photoinhibition competes with the photochemical quenching. The analysis of the time-scale of the photosynthetic reaction centres as a function of the irradiance allows interpreting the performances of photobioreactors characterized by non-homogeneous irradiance.

Alkaline direct transesterification of different species of Stichococcus for bio-oil production.

The cost of bio-oil refining from microalgal biomass can be significantly reduced by combining extraction and transesterification. The characterisation and optimisation of the combined steps have been carried out on strains of Stichococcus bacillaris, focusing on catalyst type and concentration, reaction time and temperature, methanol/biomass ratio, pre-mixing time and water content in the biomass. The bio-oil yield has been referenced as production of fatty acid methyl esters (FAMEs). The maximum yield (∼17%) was achieved using dried biomass with alkaline catalyst at 60°C and methanol/biomass weight ratio of 79:1. Alkaline catalyst conditions gave faster reaction rates and higher bio-oil yields than acid catalyst. Yield was also strongly affected by water content in the biomass. A mechanistic interpretation has been proposed to elucidate the effect of the different operating conditions. However, the structural characteristics of the Chlorophyta cell wall can be very different, leading to different bio-oil yields when the same protocol is applied. Therefore, the optimised protocol of direct transesterification for Stichococcus bacillaris strains was tested on other Stichococcus strains and several other Chlorophyta species characterised by a different cell wall structure. It was clearly demonstrated that different results for bio-oil yield were obtained within the same microalgal species and much more within different microalgal genera.

Sustainable bio-hydrothermal sequencing treatment for asbestos-cement wastes

In this paper, the treatment of asbestos-cement waste (ACW) has been attempted by a dark fermentation (DF) pre-treatment followed by hydrothermal and anaerobic digestion (AD) treatments. During DF, glucose, employed as a biodegradable substrate, was mainly converted to H2-rich biogas and organic acids (OAs). The latter caused the dissolution of the cement matrix and the partial structural collapse of chrysotile (white asbestos). To complete the chrysotile degradation, hydrothermal treatment of the DF effluents was performed under varying operating conditions (temperature, acid type, and load). After the addition of 5.0 g/L sulfuric acid, a temperature decrease, from 80 °C to 40 °C, slowed down the treatment. Similarly, at 100 °C, a decrease of sulfuric, lactic or malic acid load from 5.0 g/L to 1.0 g/L slowed down the process, regardless of acid type. The acid type did not affect the hydrothermal treatment but influenced the AD of the hydrothermal effluents. Indeed, when malic acid was used, the AD of the hydrothermally treated effluents resulted in the highest production of methane. At the end of the AD treatment, some magnesium ions derived from ACW dissolution participated in the crystallization of struvite, an ecofriendly phosphorous-based fertilizer.