Automated H2O2 monitoring during photo-Fenton processes using an Arduino self-assembled automatic system.

A cheap and easy to use Arduino self-assembled automatic system was employed to continuously monitor the hydrogen peroxide consumption during the photo-Fenton degradation of caffeine, selected as model target compound. The automatic system made it possible to measure the H2O2 concentration in the reaction cell via a colorimetric reaction and to take samples for HPLC analysis minimising the operator manual intervention and exposure to UV radiation. The obtained results were compared in terms of LOD and LOQ with H2O2 measurements manually performed using UV-Vis spectrophotometry, evidencing better analytical performance when using the automatic system; LOD and LOQ were respectively 0.032 mM and 0.106 mM for the automatic system against 0.064 mM and 0.213 mM for UV-Vis spectrophotometry. Furthermore, the photo-Fenton treatment was optimised by means of a Design of Experiments (DoE) investigating the effect of added H2O2 concentration, iron concentration and caffeine initial concentration on system performances. The use of the automatic device for such monitoring provided several advantages: automation (with consequent reduction of the workload), measurement increased precision, reduced reagents consumption and waste production in agreement with the principles of Green Analytical Chemistry.

Application of Fe(III)-EDDS complexes and soybean peroxidase in photo-Fenton processes for organic pollutant removal: insights into possible synergistic effects.

Photo-Fenton processes activated by biodegradable Fe(III)-EDDS complexes have attracted huge attention from the scientific community, but the operative mechanism of the photo-activation of H2O2 in the presence of Fe(III)-EDDS has not been fully clarified yet. The application of the Fe(III)-EDDS complex in Fenton and photo-Fenton (mainly under UV-B light) processes, using 4-chlorophenol (4-CP) as a model pollutant was explored to give insights into the operative mechanism. Furthermore, the potential synergistic contribution of soybean peroxidase (SBP) was investigated, since it has been reported that upon irradiation of Fe(III)-EDDS the production of H2O2 can occur. SBP did not boost the 4-CP degradation, suggesting that the possibly produced H2O2 reacts immediately with the Fe(II) ion with a quick kinetics that does not allow the diffusion of H2O2 into the bulk of the solution (i.e., outside the solvent cage of the complex). So, a concerted mechanism in which the photochemically produced H2O2 and Fe(II) react inside the hydration sphere of the Fe(III)-EDDS complex is proposed.

Environmental Assessment of Solar Photo-Fenton Processes at Mild Condition in the Presence of Waste-Derived Bio-Based Substances.

The assessment of environmental sustainability has assumed great importance during the study and implementation of a new process, including those aimed to waste valorization and reuse. In this research, the environmental performance of the photo-Fenton processes was evaluated using the life cycle assessment (LCA) methodology. In particular, photo-Fenton conducted in mild conditions (almost neutral pH), using soluble bio-organic substances as auxiliary agents were compared with the "classic" photo-Fenton run at pH 2.8. The evaluation was carried out both, at the laboratory level and at pilot plant scale. LCA analysis shows that working in mild conditions reduces the environmental burden associated with the use of chemicals. On the other hand, the occurring drop in effectiveness significantly increases the overall impact, thus evidencing the need of considering the process as a whole.

The "Lab4treat" Outreach Experience: Preparation of Sustainable Magnetic Nanomaterials for Remediation of Model Wastewater.

The Lab4treat experience has been developed to demonstrate the use of magnetic materials in environmental applications. It was projected in the frame of the European project Mat4Treat, and it was tested several times in front of different audiences ranging from school students to the general public in training and/or divulgation events. The experience lends itself to discuss several aspects of actuality, physics and chemistry, which can be explained by modulating the discussion depth level, in order to meet the interests of younger or more experienced people and expand their knowledge. The topic is relevant, dealing with the recycling of urban waste and water depollution. The paper is placed within the field of water treatment for contaminant removal; therefore, a rich collection of recent (and less recent) papers dealing with magnetic materials and environmental issues is described in the Introduction section. In addition, the paper contains a detailed description of the experiment and a list of the possible topics which can be developed during the activity. The experimental approach makes the comprehension of scientific phenomena effective, and, from this perspective, the paper can be considered to be an example of interactive teaching.

Evaluation of the Photocatalytic Activity of a Cordierite-Honeycomb-Supported TiO2 Film with a Liquid-Solid Photoreactor.

Anatase nanoparticles in suspension have demonstrated high photoactivity that can be exploited for pollutant removal in water phases. The main drawback of this system is the difficulty of recovering (and eventually reusing) the nanoparticles after their use, and the possible interference of inorganic salts (e.g., sulfates) that can reduce the performance of the photocatalyst. The present work describes the development of a cordierite-honeycomb-supported TiO2 film to eliminate the problems of catalyst recovery. The catalyst was then tested against phenol in the presence of increasing concentrations of sulfates in a specially developed recirculating modular photoreactor, able to accommodate the supported catalyst and scalable for application at industrial level. The effect of SO42- was evaluated at different concentrations, showing a slight deactivation only at very high sulfate concentration (≥3 g L-1). Lastly, in the framework of the EU project Project Ô, the catalyst was tested in the treatment of real wastewater from a textile company containing a relevant concentration of sulfates, highlighting the stability of the photocatalyst.

Use of Low-Cost Magnetic Materials Containing Waste Derivatives for the (Photo)-Fenton Removal of Organic Pollutants.

Hybrid magnetite/maghemite nanoparticles (MNP) coated with waste-sourced bio-based substances (BBS) were synthesized and studied for the degradation of phenol, chosen as a model pollutant, in water. A systematic study was undertaken in order to rationalize MNP-BBS behavior and optimize their performance. The effect of experimental parameters, such as light irradiation, addition of hydrogen peroxide, and the ratio between hydrogen peroxide and MNP-BBS concentrations, was studied. The generation of hydroxyl radicals was assessed, and the recovery and re-cycle of the material was investigated. Our results indicate that phenol degradation could be attained by both Fenton and photo-Fenton processes, with higher efficiency in dark condition and in the presence of a suitable amount of hydrogen peroxide. Evidence was obtained for the roles of iron ions leached from the materials as well as of organic matter released in the solution upon partial photodegradation of the organic coating. The reusability tests indicated a lower but still valid performance of the material. Optimization of the experimental conditions was performed to achieve the highest efficiency in substrate degradation, and fundamental insights into the mechanism of the MNP-BBS Fenton-like reaction were obtained.

Photo-Fenton Degradation of Pentachlorophenol: Competition between Additives and Photolysis.

In the present work, the photo-Fenton degradation of pentachlorophenol (PCP, 1 mg/L) has been studied under simulated and natural solar irradiation; moreover, the effect on the process efficiency of urban waste-derived soluble bio-based substances (SBO), structurally comparable to humic acids, has been investigated. Experiments showed a crucial role of PCP photolysis, present in the solar pilot plant and hindered by the Pyrex® filter present in the solar simulator. Indeed, the SBO screen negatively affects PCP degradation when working under natural solar light, where the photolysis of PCP is relevant. In contrast, in the absence of PCP photolysis, a significant improvement of the photo-Fenton process was observed when added to SBO. Furthermore, SBO were able to extend the application of the photo-Fenton process at circumneutral pH values, due to their ability to complex iron, avoiding its precipitation as oxides or hydroxides. This positive effect has been observed at higher concentration of Fe(II) (4 mg/L), whereas at 1 mg/L, the degradation rates of PCP were comparable in the presence and absence of SBO.

Sustainable Magnetic Materials (from Chitosan and Municipal Biowaste) for the Removal of Diclofenac from Water.

The photodegradation of an aqueous solution of diclofenac (DCF) has been attempted in the presence of hydrogen peroxide and organic/inorganic hybrid magnetic materials under simulated and real solar light. The hybrid magnetic materials have been prepared via coprecipitation synthesis starting from iron(II) and iron(III) inorganic salts in the presence of bioderived organic products (i.e., chitosan or bio-based substances isolated from commercially available composted urban biowastes) acting as stabilizers of the iron-containing phase. In addition to the as prepared hybrid materials, the corresponding materials obtained after a pyrolytic step at low temperature (550 °C) have been tested. The obtained results evidenced the capability of the materials to activate hydrogen peroxide at mild pH promoting DCF (photo) degradation. All the materials feature also as adsorbents since a decrease of DCF is observed also when working in the dark and in the absence of hydrogen peroxide.

Green Waste-Derived Substances Immobilized on SBA-15 Silica: Surface Properties, Adsorbing and Photosensitizing Activities towards Organic and Inorganic Substrates.

Urban wastes are a potential source of environment contamination, especially when they are not properly disposed. Nowadays, researchers are finding innovative solutions for recycling and reusing wastes in order to favour a sustainable development from the viewpoint of circular economy. In this context, the lignin-like fraction of biomass derived from Green Compost is a cost-effective source of soluble Bio-Based Substances (BBS-GC), namely complex macromolecules/supramolecular aggregates characterized by adsorbing and photosensitizing properties. In this work BBS-GC were immobilized on a silica support (SBA-15) and the chemico-physical properties of the resulting hybrid material (BBS-SBA) were analysed by zeta-potential measurements, nitrogen adsorption at 77K and micro-calorimetric techniques. Successively, the BBS-SBA photosensitizing and adsorption abilities were tested. Adsorption in the dark of Rhodamine B and Orange II on BBS-SBA and their degradation upon irradiation under simulated solar light were shown, together with the formation of hydroxyl radicals detected by Electron Paramagnetic Resonance spectroscopy. Furthermore, the adsorption of six inorganic ions (Al, Ni, Mn, As, Hg, Cr) on BBS-SBA was studied in pure water at two different pH values and in a landfill leachate, showing the good potential of this kind of materials in the removal of wastewater contaminants.

New Insights on the Photodegradation of Caffeine in the Presence of Bio-Based Substances-Magnetic Iron Oxide Hybrid Nanomaterials.

The exploitation of organic waste as a source of bio-based substances to be used in environmental applications is gaining increasing interest. In the present research, compost-derived bio-based substances (BBS-Cs) were used to prepare hybrid magnetic nanoparticles (HMNPs) to be tested as an auxiliary in advanced oxidation processes. Hybrid magnetic nanoparticles can be indeed recovered at the end of the treatment and re-used in further water purification cycles. The research aimed to give new insights on the photodegradation of caffeine, chosen as marker of anthropogenic pollution in natural waters, and representative of the contaminants of emerging concern (CECs). Hybrid magnetic nanoparticles were synthetized starting from Fe(II) and Fe(III) salts and BBS-C aqueous solution, in alkali medium, via co-precipitation. Hybrid magnetic nanoparticles were characterized via X-ray diffraction (XRD), thermo-gravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The effect of pH, added hydrogen peroxide, and dissolved oxygen on caffeine photodegradation in the presence of HMNPs was assessed. The results allow for the hypothesis that caffeine abatement can be obtained in the presence of HMNPs and hydrogen peroxide through a heterogeneous photo-Fenton mechanism. The role of hydroxyl radicals in the process was assessed examining the effect of a selective hydroxyl radical scavenger on the caffeine degradation kinetic.

New Route for Valorization of Oil Mill Wastes: Isolation of Humic-Like Substances to be Employed in Solar-Driven Processes for Pollutants Removal.

The valorization of olive oil mill solid wastes (OMW) has been addressed by considering it as a possible source of humic-like substances (HLSs), to be used as auxiliary substances for photo-Fenton, employing caffeine as a target pollutant to test the efficiency of this approach. The OMW-HLS isolation encompassed the OMW basic hydrolysis, followed by ultrafiltration and drying. OMW-HLS structural features have been investigated by means of laser light scattering, fluorescence, size exclusion chromatography, and thermogravimetric analysis; moreover, the capability of OMW-HLS to generate reactive species under irradiation has been investigated using spin-trap electronic paramagnetic resonance. The caffeine degradation by means of photo-Fenton process driven at pH = 5 was significantly increased by the addition of 10 mg/L of OMW-HLS. Under the mechanistic point of view, it could be hypothesized that singlet oxygen is not playing a relevant role, whereas other oxidants (mainly OH• radicals) can be considered as the key species in promoting caffeine degradation.

Sustainable magnet-responsive nanomaterials for the removal of arsenic from contaminated water.

In this study, chitosan and bio-based substances (BBS) obtained from composted biowaste were used as stabilizers for the synthesis of magnet-sensitive nanoparticles (NPs) via coprecipitation method. A pyrolysis treatment was carried out on both biopolymers at 550°C, and their consequent conversion into a carbon matrix was followed by means of different physicochemical characterization techniques (mainly FTIR spectroscopy and XRD), whereas magnetic properties were evaluated by magnetization curves. The prepared materials were tested in water remediation processes from arsenic (As) species (both inorganic and organic forms). These tests, explained by means of the most common adsorption models, evidenced that the best performances were reached by both materials obtained after pyrolysis treatments, pointing out the promising application of such magnet-sensitive materials as easy-recoverable tools for water purification treatments.

Paramagnetic iron-doped hydroxyapatite nanoparticles with improved metal sorption properties. A bioorganic substrates-mediated synthesis.

This paper describes the synthesis of paramegnetic iron-containing hydroxyapatite nanoparticles and their increased Cu(2+) sorbent capacity when using Ca(2+) complexes of soluble bioorganic substrates from urban wastes as synthesis precursors. A thorough characterization of the particles by TEM, XRD, FTIR spectroscopy, specific surface area, TGA, XPS, and DLS indicates that loss of crystallinity, a higher specific area, an increased surface oxygen content, and formation of surface iron phases strongly enhance Cu(2+) adsorption capacity of hydroxyapatite-based materials. However, the major effect of the surface and morphologycal modifications is the size diminution of the aggregates formed in aqueous solutions leading to an increased effective surface available for Cu(2+) adsorption. Maximum sorption values of 550-850 mg Cu(2+) per gram of particles suspended in an aqueous solution at pH 7 were determined, almost 10 times the maximum values observed for hydroxyapatite nanoparticles suspensions under the same conditions.

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.

High-performance liquid chromatography coupled to ultraviolet diode array detection and electrospray ionization mass spectrometry for the analysis of intermediates produced in the initial steps of the photocatalytic degradation of sulfonated azo dyes.

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.

Photocatalytic oxidation of methyl-orange in aqueous suspension: comparison of the performance of different polycrystalline titanium dioxide.

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.