Assessing the phototransformation of diclofenac, clofibric acid and naproxen in surface waters: Model predictions and comparison with field data.

Phototransformation is important for the fate in surface waters of the pharmaceuticals diclofenac (DIC) and naproxen (NAP) and for clofibric acid (CLO), a metabolite of the drug clofibrate. The goal of this paper is to provide an overview of the prevailing photochemical processes, which these compounds undergo in the different conditions found in freshwater environments. The modelled photochemical half-life times of NAP and DIC range from a few days to some months, depending on water conditions (chemistry and depth) and on the season. The model indicates that direct photolysis is the dominant degradation pathway of DIC and NAP in sunlit surface waters, and potentially toxic cyclic amides were detected as intermediates of DIC direct phototransformation. With modelled half-life times in the month-year range, CLO is predicted to be more photostable than DIC or NAP and to be degraded mainly by reaction with the •OH radical and with the triplet states of chromophoric dissolved organic matter (3CDOM*). The CLO intermediates arising from these processes and detected in this study (hydroquinone and 4-chlorophenol) are, respectively, a chronic toxicant to aquatic organisms and a possible carcinogen for humans. Hydroquinone is formed with only ∼5% yield upon CLO triplet-sensitised transformation, but it is highly toxic for algae and crustaceans. In contrast, the formation yield of 4-chlorophenol reaches ∼50% upon triplet sensitisation and ∼10% by ·OH reaction. The comparison of model predictions with field data from a previous study yielded a very good agreement in the case of DIC and, when using 4-carboxybenzophenone as proxy for triplet sensitisation by CDOM, a good agreement was found for CLO as well. In the case of NAP, the comparison with field data suggests that its direct photolysis quantum yield approaches or even falls below the lower range of literature values.

Selective porous gates made from colloidal silica nanoparticles.

Highly selective porous films were prepared by spin-coating deposition of colloidal silica nanoparticles on an appropriate macroporous substrate. Silica nanoparticles very homogenous in size were obtained by sol-gel reaction of a metal oxide silica precursor, tetraethyl orthosilicate (TEOS), and using polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers as soft-templating agents. Nanoparticles synthesis was carried out in a mixed solvent system. After spin-coating onto a macroporous silicon nitride support, silica nanoparticles were calcined under controlled conditions. An organized nanoporous layer was obtained characterized by a depth filter-like structure with internal porosity due to interparticle voids. Permeability and size-selectivity were studied by monitoring the diffusion of probe molecules under standard conditions and under the application of an external stimulus (i.e., electric field). Promising results were obtained, suggesting possible applications of these nanoporous films as selective gates for controlled transport of chemical species in solution.

Activation of persulfate by irradiated magnetite: implications for the degradation of phenol under heterogeneous photo-Fenton-like conditions.

We show that phenol can be effectively degraded by magnetite in the presence of persulfate (S2O8(2­)) under UVA irradiation. The process involves the radical SO4(­â€¢), formed from S2O8(2­) in the presence of Fe(II). Although magnetite naturally contains Fe(II), the air-exposed oxide surface is fully oxidized to Fe(III) and irradiation is required to produce Fe(II). The magnetite + S2O8(2­) system was superior to the corresponding magnetite + H2O2 one in the presence of radical scavengers and in a natural water matrix, but it induced phenol mineralization in ultrapure water to a lesser extent. The leaching of Fe from the oxide surface was very limited, and much below the wastewater discharge limits. The reasonable performance of the magnetite/persulfate system in a natural water matrix and the low levels of dissolved Fe are potentially important for the removal of organic contaminants in wastewater.

Phototransformation pathways of the fungicide dimethomorph ((E,Z) 4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-oxo-2-propenyl]morpholine), relevant to sunlit surface waters.

Dimethomorph (DMM) is a widely used fungicide that shows low toxicity for birds and mammals but can be quite toxic to aquatic organisms. The persistence of DMM in surface waters is thus of high importance, and this work modelled its water half-life time due to photochemical processes. Depending on environmental conditions (e.g. water chemistry, depth, season), DMM lifetime could vary from a few days to a few months. For lifetimes of a few weeks or shorter, photochemistry would be an important pathway for DMM attenuation in surface waters. Such conditions could be reached in summer, in shallow water bodies with low dissolved organic carbon (DOC) and high nitrate and/or nitrite. The main pathways accounting for DMM photodegradation in environmental waters would be the reactions with OH and with the triplet states of chromophoric dissolved organic matter, (3)CDOM* (under the hypothesis that (3)CDOM* reactivity is well described by the triplet state of anthraquinone-2-sulphonate), while direct photolysis would be less important. The OH pathway would be favoured in low-DOC waters, while the opposite conditions would favour (3)CDOM*. It was possible to detect and identify some intermediates formed upon reaction between DMM and (3)CDOM*, namely N-formylmorpholine, 4-chloroacetophenone and 4-chlorobenzoic acid. The transformation of DMM into the detected compounds would not increase the acute toxicity of the fungicide towards mammals, and the acute effects for freshwater organisms could be decreased significantly.

Hernia-repair prosthetic devices functionalised with chitosan and ciprofloxacin coating: controlled release and antibacterial activity.

Polypropylene nets are widely used as hernioplasty prostheses. The reproduction of bacteria within the net fibers intersections can occur after the application of the prosthesis causing infections. For this reason, bacteria have to be removed in the very early stage of surgical implantation. Activation of the prosthesis surface was done by an innovative oxidizing plasma treatment (APP-DBD) working under atmospheric conditions in order to favor the deposition of an antibacterial coating of chitosan (biocompatible carbohydrate) and ciprofloxacin (broad spectrum antibiotic). Two different coating mixtures were realised and the antibacterial properties of such functionalised nets were investigated, together with their effectiveness. Physico-chemical characterisations of meshes were carried out before and after functionalisation by SEM-EDS and infrared spectroscopy. The release of both chitosan and ciprofloxacin, under controlled experimental conditions, was followed respectively by colorimetric determination (using UV-Visible spectroscopy) and chromatographic analysis (using HPLC). In vitro tests allow verifying antimicrobial activity (inoculation of specimens in a Staphylococcus aureus suspension).

Waste-derived bioorganic substances for light-induced generation of reactive oxygenated species.

Urban waste-derived bioorganic substances (UW-BOS) have shown promise as chemical auxiliaries for a number of technological applications in the chemical industry and in environmental remediation. In this study, the application of these substances in the photodegradation of organic pollutants is addressed. The experimental work is specifically focused on the photolysis mechanism promoted by AC8, a UW-BOS isolated from a 2:1 w/w mixture of food and green residues, composted for 110 days, using 4-chlorophenol (4-CP) as probe molecule. The production of (⋅)OH and the ¹O2 is monitored by EPR spectroscopy. The correlation between radical species evolution and photodegradation of 4-CP is investigated. The effect of ¹O2 and (⋅)OH scavengers on the 4-CP degradation process is also checked. The results suggest that the role of these species in the photodegradation of 4-CP depends on AC8 concentration. AC8 is thereby proven to be a photosensitizer for applications in environmental remediation. The results on AC8 further support the use of urban bio-waste as a versatile source of chemical auxiliaries of biological origin for use in diversified applications.

Oxidative degradation of Remazol Turquoise Blue G 133 by soybean peroxidase.

Reactive dyes are widely employed in textile industries and their removal from wastewaters is a relevant environmental problem. In addition to chemical and physical methods, several bioremediation approaches, involving intact micro-organisms or isolated enzymes, have been proposed to decolorize dye solutions. In this paper, we report the complete and fast decolourization of a Cu(II)-phthalocyanine based reactive dye (Remazol Turquoise Blue G 133) by means of the soybean peroxidase/H(2)O(2) system. The oxidative degradation of the dye in aqueous solution at 25°C was studied as function of pH, revealing a quantitative decolourization yield at acidic pH values with a maximum of activity at pH 3.3. The reaction products were identified and characterized by HPLC-diode array detector (DAD)-mass spectrometry (MS), ionic chromatography and EPR techniques. This analysis showed that the enzyme catalyses the breaking of the phthalocyanine ring producing sulfophthalimide as the main degradation product, and the release of stoichiometric amount of ammonium and Cu(II) ions.