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The photocatalytic degradation of carbaryl in aqueous TiO2 dispersions irradiated with simulated solar light was investigated. Complete mineralization of the pesticide to CO2 was observed, with the formation of nitrate and ammonium ions as nitrogen-containing end products. Various aromatic intermediates, detected during the process, were identified using HPLC and GC−MS techniques, and their kinetic evolution was also investigated. The formation of the transient compound 1,3-indandione, more persistent than carbaryl, was observed. From obtained analytical and kinetic data, a possible reaction scheme was proposed.

Food wastes are shown as a cost-effective source of added-value products for a wide number of uses. For soluble substances isolated from municipal biowastes, the present chapter reviews work performed in the last 7 years investigating the chemical nature, the physical-chemical properties, and the performance in chemical and environmental technologies, in material chemistry and in agriculture. Very recent unpublished data are also reported to show that ongoing research is a worthwhile effort to realise the full potential of the above refuse-derived biobased products. The available data allow a viable situation to be envisioned where urban waste-treatment plant are turned into biorefinery for the production of energy, chemicals and consumer products with friendly environmental impact. The perspectives for this scenario to become real are discussed.

A bio-organic substances (BOS) was isolated from urban bio-refuse undergoing aerobic biodegradation. The isolated BOS was characterized for chemical composition and performance as sensitizers for the photodegradation of azo-dyes in solution. Three commercial sulphonated azo-dyes, i.e., ethylorange (EO), Orange I (OI) and Orange II (OII), were selected as probe molecules. For these molecules high abatement rates (60–100%) were obtained within few hours of irradiation in the presence of BOS, whereas almost no abatement was observed in the absence of BOS. A delay in the color bleaching was observed, in comparison to the dyes degradation; coloured intermediates were identified. Acute toxicity tests showed a low toxicity for the samples at the end of the degradation process.

Surfactant-assisted soil washing and photocatalysis are well-known remediation processes of environmental concern. The application of photocatalysis to treat soil washing extracts containing 4-methylphenol, 4-ethylphenol and 4-tert-butylphenol in the presence of nonionic (C(12)E(8) and C(12)E(23)) and anionic (SDS) surfactants and some of their binary mixtures was investigated in this work by studying the pollutants degradation in the presence of TiO(2) dispersions irradiated with simulated solar light.Clean soil samples were spiked with the investigated alkylphenols. Aqueous solutions of the chosen surfactants were placed in contact for some hours with the spiked soil samples in a rotatory mixer. The pollutants recoveries were evaluated via HPLC analysis. Photocatalytic experiments were performed in solarbox on aqueous solutions and on aqueous surfactant solutions containing the pollutants.The pollutants removal from the soil was proven effective using the examined surfactant solutions. The photocatalytic treatment of the wastes was faster using Brij 35, but also SDS and C(12)E(8)-SDS mixtures can be applied. After 2-5 h the complete pollutants abatement was obtained, depending on the surfactant chosen and on the amount of TiO(2) employed. On the contrary, the treatment of wastes containing C(12)E(8) was an extremely slow process.The photocatalytic approach can be applied to remove the examined aromatic pollutants from the washing wastes, confirming the viable coupling between this advanced oxidation method and the surfactant-based soil remediation treatments. Surfactant adsorption onto TiO(2) and micelles concentration play a dominant role.

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.

Traces of aluminium were preconcentrated in water samples by forming a complex with lumogallion, and successfully accumulated in the micellar phase obtained from cationic or non-ionic surfactants and filtered through 10 000 molecular weight cut-off ultrafiltration membranes. Studies indicated that, at pH 5.9, with 1 X 10 −3 M lumogallion and 2 X 10 −2 M cetyltrimethylamonium bromide, quantitative retention of aluminium present at μg ml −1 concentration levels was achieved. A micellar-enhanced fluorimetric procedure was employed to analyse the permeate solutions, whereas nitrous oxide-acetylene flame atomic emission spectrometry was used to determine aluminium in the retentate. The experimental parameters that influence the micellar-enhanced ultrafiltration (MEUF) efficiency were investigated and the analytical procedures were optimized. the MEUF of trace levels of aluminium allows for either preconcentration of the analyte or enhancement of the emission signals.

To promote bio-based products for the industry, six bio-organic substances (cHALi) isolated from yard trimmings (green) and food (humid) urban residues aged under aerobic digestion for 0–60 days were investigated for their potential to perform as sensitizers for azo-dyes photodegradation. Ethylorange (EO) was used as probe molecule at 5 mg L −1 starting concentration and irradiated in a closed Pyrex ® cell with a Xenon (1500 W) lamp and a cut-off filter for wavelengths below 340 nm or in a cylindrical photochemical reactor equipped with a 125 W medium pressure Hg lamp. The cHALi/EO ratio in the starting EO solution varied in the 0–200 (w/w) range. The % dye abatement was found a function of the irradiation time, of the type of cHALi substance and of the cHALi/EO ratio. The best results were achieved with cHALi isolated after 7 days biomass aerobic digestion. Total dye abatement was achieved within relatively short few hours. A progressive dye mineralization was observed under the same experimental conditions. On the contrary no significant degradation was evident for the cHALi substances within the same irradiation time. Several hydroxylated azo compounds were identified as likely responsible of residual color after total EO abatement. The results, coupled to the previously reported good performance of the same cHALi substances as auxiliaries for textile dyeing, augur well for the development of both efficient and environmentally friendly textile dyeing processes.

Quantitative removal of uranyl ions present in aqueous solutions at the μg ml −1 concentration level was achieved using the micellar-enhanced ultrafiltration technique. Suitable chelating micelles were formed by dissolving selective hydrophobic acyclic ligands in the usual amphiphilic aggregates. These ligand-doped miceles accumulate the uranyl ions through the formation of tightly bound chelates. The aggregates and their guest metal complexes were successively separated by ultrafiltration through hydrophilic membranes of suitable pore size. The efficiency of the process is related to the affinity of the ligands for the micelles. Non-ionic and cationic surfactants were investigated. Quantitative retention of the analyte in the surfactant-rich retente solution was achieved when working with cetyltrimethylammonium bromide micelles. The uranyl recovery was significantly increased by introducing trioctylphosphine oxide as an auxiliary ligand, which allowed for very efficient preconcentrations at lower pH.

The effect of simulated solar light on nitrobenzene degradation in Fe⁺³ /H₂ O₂ solutions was investigated under different experimental conditions. Consumption profiles of NBE and H₂ O₂ display an autocatalytic kinetic behavior for both dark and photo-assisted degradation experiments. The rates of the initial slow phase that precedes the catalytic phase are significantly enhanced by irradiation, although the effect of simulated solar light on the rates of the fast phase is negligible. The absolute rates of the slow phase increase with the concentrations of Fe⁺³ and H₂ O₂ , whereas the initial rate of the degree of conversion increase decreases with organic matter loading. The reaction progress was characterized by HPLC, GC–MS, IC, TOC (total organic carbon) and toxicity analyses. The main products detected were 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, 1,3-dinitrobenzene, phenol, oxalic acid, formic acid, NO₂ − and NO₃ − . Product distribution profiles are discussed in connection with TOC and toxicity measurements. The results show that dark treatment is neither capable of lowering the organic content nor capable of reducing the effluent toxicity to acceptable levels. On the other hand, photo-assisted processes induced by simulated solar light can significantly enhance both mineralization and detoxification efficiencies., Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas

High-performance liquid chromatography coupled to ultraviolet diode array detection and electrospray ionization mass spectrometry was applied to monitor the photocatalytic degradation mediated by TiO2 of three sulfonated monoazo dyes (Orange I, Orange II, and Ethylorange) present in aqueous solution. Photobleaching, organic carbon, nitrogen and sulfur evolution were also followed during the process. Delayed carbon mineralization was observed with respect to both dyes disappearance and photobleaching, due to the formation of transient intermediate compounds which were in turn completely degraded. Among the intermediates produced during the initial degradation steps the formation of several hydroxylated derivatives, mostly coloured, was evidenced. The MS(2) spectra allowed one to formulate hypothesis about the OH attack positions; a peculiar reactivity of the azo moiety was shown by Orange I and Orange II.

The effect of sodium dodecyl sulphate (SDS) on the photocatalytic degradation of 2,4,5-trichlorophenol (2,4,5-TCP) in aqueous TiO2 dispersions under irradiation with simulated AM1 solar light was investigated. A peculiar kinetic behaviour was observed, with increasing inhibition of the substrate degradation as a function of SDS concentration below the critical micellar concentration (cmc), followed by a subsequent faster degradation around this concentration range and a further degradation rate decrease above the cmc. The role of surfactant adsorption onto the suspended semiconductor and the disaggregation of TiO2 microparticles seems to be crucial. The complete degradation of the investigated substrate, still achievable in the presence of SDS without relevant changes in the reaction mechanism, was confirmed suggesting the possible application of photocatalysis for the treatment of surfactant-containing wastes.

The photocatalytic oxidation of methyl-orange (C14H14N3SO3Na) dye was carried out in aqueous suspensions of polycrystalline TiO2 irradiated with artificial light until its complete mineralization was achieved. The performances of two widely used semiconductor powders were studied for comparison purposes. The dependence of dye photo-oxidation rate on various experimental parameters, including substrate concentration, semiconductor amount, and pH was investigated by using both catalysts. The observed dye degradation rates followed pseudo-first order kinetics with respect to the substrate concentration under the experimental conditions used. The two investigated TiO2 powders (Degussa P25 and Merck) showed different photoactivities. TOC analyses confirmed the complete mineralization achievable using both photocatalysts. Three main transient products still maintaining the chromophoric azo group were identified prior to their transformation into other degradation products which are non-absorbing in the visible region.

A procedure to extract polycyclic aromatic hydrocarbons (PAHs) from a contaminated river sediment is discussed; this combines short extraction times obtained by microwave energy with the peculiar solvent capability of aqueous micellar solutions. The technique, named microwave-assisted micellar extraction (MAME), was tested for the extraction of 11 PAHs from a spiked river sediment using polyoxyethylene (23) dodecyl ether (Brij 35), polyoxyethylene (10) dodecyl ether (C 12 E 10 ) or cetyl trimethylammonium bromide (CTAB). Different temperatures and extraction times were explored to establish whether this method has merit. Comparative measurements were made using sonication and Soxhlet extraction with acetone-hexane. Generally, Soxhlet extraction was revealed to be the most effective method to extract the PAHs from the solid matrix, with percent of recovery ranging from 92% to 102%. Nevertheless, high recoveries were also achieved by MAME using C 12 E 10 ; in fact, with only the exception of indeno[1,2,3- c...

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almeria” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H2O2, S2O82−) and some ions (Cl−, SO42−) on the process was also studied.

The photocatalytic degradation of the anthraquinonic dye Acid Blue 80 in aqueous solutions containing TiO2 dispersions has been investigated. The process has been monitored by following either the disappearance of the dye (via HPLC) and the formation of its end-products (via IC, GC, and TOC analysis). Although a relatively fast decolorization of the solutions has been observed, the mineralization is slower, and the presence of residual organic compounds was evidenced even after long term irradiation, confirming the relevant stability of anthraquinone derivatives. The identification of various unstable intermedi ates formed after low irradiation times was performed by HPLC-MS, allowing us to give insight into the early steps of the degradation process which mainly involve C−N bonds breaking and substrate hydroxylation. Complete and relatively fast mineralization of the substrate was achieved by irradiating the semiconductor dispersions in the presence of added K2S2O8.

The possible use of flow injection (FI) to monitor the photocatalytic mineralization of dicamba (3,6-dichloro-2-methoxybenzoic acid) present at the trace level in aqueous solutions containing TiO2 suspensions has been evaluated. Experiments were performed in a stirred photochemical reactor equipped with a simple FI manifold, integrating an online filtration unit able to perform the monitoring of the UV absorbance of the irradiated solution every 4 min. The light source used was a medium pressure mercury lamp (125 W). During the initial steps of the reaction the formation of UV absorbing intermediates, which completely disappear in less than 80 min, was evidenced. Additional HPLC, DOC and chloride ion measurements carried out on manually taken samples confirmed the complete mineralization of dicamba within about 90 min. The proposed on-line monitoring looks particularly suitable for the control of degradation treatments where primary degradation and mineralization steps take place after a comparable irradiation time.

The photocatalytic degradation of 2,3,6-trichlorobenzoic acid (2,3,6-TBA) in aqueous TiO2 dispersions irradiated with simulated solar light was investigated. Fast primary degradation of the herbicide, which obeys a pseudo-first order law, was observed. Complete mineralisation of the organic carbon to CO2 was obtained after long term irradiation, with corresponding stoichiometric transformation of organic chlorine into chloride ion. Various aromatic intermediates, originating from 2,3,6-TBA, were detected during the treatment and identified using GC-MS. From the analytical data, a possible multi-step degradation scheme was proposed. The photocatalytic treatment of the pesticide was also performed in the presence of Brij 35 micellar solutions, although strong inhibition of the process was observed. When surfactant aggregates are present the photocatalytic destruction of 2,3,6-TBA is still possible at reasonable rates only after a proper dilution of the waste and by increasing significantly the semiconductor/pollutant ratio.

The photocatalytic degradation of several aniline derivatives present in aqueous solutions containing TiO2 suspensions was investigated. The process leads to the complete and fast decomposition (within about 1 h) of the pollutant molecules, promoted by oxidizing radical species formed at the irradiated semiconductor/water interface. The stoichiometric formation of CO2 from the organic carbon was assessed, whereas other inorganic end-products were detected depending on the nature of the aniline substituents. Unstable hydroxyaromatic intermediates were also identified during the initial steps of the treatment. The primary degradation, which follows pseudo-first-order kinetics, changes with the aniline substituents and is strongly dependent on pH.

Chelating aggregates consisting of Triton X100 host micelles and hydrophobic derivatives of PAN have been examined as suitable candidates for preconcentration and selective separation of transition metal ions through micellar-enhanced ultrafiltration. The effective accumulation in the surfactant-rich retentate of nickel(II), copper(II), cobalt(II), manganese(II) and zinc(II), present at trace levels in aqueous samples, has been achieved by operating at pH ca. 6 with a ligand having a binding constant to the host micelles higher than 2000 l./mol. The efficient separation of micelle-bound metal chelates from unreactive ions has been assessed, together with the feasibility of selective enrichment and purification of the investigated metal ions present in mixtures through a multistage process.

This study aims to investigate how the photocatalytic efficiency of zinc oxide can be improved by introducing doping species into its crystal lattice. New materials based on zinc oxide doped with iron, have been synthesized using different methods, characterized and tested toward the abatement of selected organic molecules. The different synthetic strategies followed comprised sol-gel, precipitation and hydrothermal processes, in order to identify which one is capable of guaranteeing the best photocatalytic performances. The photoactivity of the new semiconductors was firstly tested using phenol as a model molecule subjected to irradiation under UV-A light. Phenol abatement is particularly favoured when using ZnO prepared via hydrothermal method and doped with iron at 0.5%. These materials were then tested toward the elimination of ketoprofen, an emerging pollutant substance, from water and real wastewater. Ketoprofen and its transformation products are completely abated within 30 min in pure water or in 1 h in wastewater.

Antifungal azoles are the most frequently used fungicides worldwide and occur as active ingredients in many antifungal pharmaceuticals, biocides, and pesticides. Azole fungicides are frequent environmental contaminants and can affect the quality of surface waters, groundwater, and drinking water. This study examined the potential of combined vacuum UV (185 nm) and UVC (254 nm) irradiation (VUV/UVC) of the azole fungicide tebuconazole and the transformation product 1,2,4-trizole on degradation and changes in ecotoxicity. In vivo ecotoxicity was examined before and after UV treatment using bioassays with test organisms from different trophic levels to integrate changes in biological effect of the parent compound and the degradation products. The test battery included the luminescent bacterium Aliivibrio fischeri, the Gram-positive bacterium Bacillus subtilis, the fungus Fusarium graminearum, the green microalga Raphidocelis subcapitata, and the crustacean Daphnia magna. The combined VUV/UVC treatment of tebuconazole in drinking water efficiently degraded the parent compound at the µg/L-mg/L level and resulted in transformation products with lower toxicity than the parent compound. A direct positive correlation was observed between the applied UV dose (fluence, J/cm2), the disappearance of tebuconazole, and the decrease in ecotoxicity. The combined VUV/UVC process does not require addition of supplementary oxidants or catalysts and our study suggests that VUV/UVC-mediated photolysis of azole fungicides in water can decrease the overall toxicity and represent a potentially environmentally friendly treatment method.

Preconcentration and removal of uranyl ions from aqueous solutions were achieved by using micellar-enhanced ultrafiltration with complexing micellar aggregates composed of Triton X-100 and different hydrophobic ligands. Derivatives of 4-aminosalicylic acid (PAS) and of 1-(2-pyridylazo)-2-naphthol (PAN) having tuned alkyl chains were used as suitable chelating agents. The selective recovery of uranyl from acid samples containing also SrII and CdII is possible using the multi-step ultrafiltration approach with the PAN derivatives, whereas effective uranyl retention can be obtained with salicylates only in neutral to basic media.

The preconcentration of aniline derivatives present in aqueous solutions containing ionic surfactants was performed using the micellar-enhanced ultrafiltration technique. The efficiency of the analyte recovery in the surfactant-rich retentate was significantly improved by exploiting the electrostatic, hydrophobic and specific interactions between the aggregates and the solute molecules. By working at low pH, in the presence of anionic micelles, the quantitative retention of amines having different substituent groups can be achieved. The enriched sample can be analysed directly using high-performance liquid chromatography.

Persistent organic pollutants have been increasingly detected in natural waters, and this represents a real challenge to the quality of this resource. To remove these species, advanced treatment technologies are required. Among these technologies, Fenton-like and photo-Fenton-like processes have been investigated for the removal of pollutants from water. Delicate aspects of photo-Fenton processes are that light-driven processes are energy intensive and require a fair amount of chemical inputs, which strongly affects their overall environmental burdens. At present, aside from determining the efficiency of the processes to remove pollutants of a particular technology, it becomes fundamental to assess also the environmental sustainability of the overall process. In this work, the methodology of the life cycle assessment (LCA) was applied to identify the hotspots of using magnetite particles covered with humic acid (Fe3O4/HA) as a heterogeneous photo-Fenton catalyst for water remediation. The sustainability of the overall process was considered, and a comparative LCA study was performed between H2O2 and persulfate activation at different pH. The addition of humic substances to the particles allows the effectiveness of the catalyst to improve without increasing the environmental impacts; these processes are strongly correlated with energy consumption and therefore with the efficiency of the process. For this reason, working at acidic pH allows us to contain the impacts.