Solar heterogeneous photo-Fenton for complete inactivation of Escherichia coli and Salmonella typhimurium in secondary-treated wastewater effluent.

In this work, complete elimination of Escherichia coli and Salmonella typhimurium was achieved in 120 min using a heterogeneous photo-Fenton process under sunlight at pH 6.5 in distilled water. A face-centered composite central design 22 with one categoric factor and three replicates at the central point was used to evaluate the effect of iron (III) oxide concentration (0.8-3.4 mg L-1), H2O2 (2-10 mg L-1), and the type of iron oxide phase (maghemite and hematite) on the inactivation of both bacteria. The results showed that the amount of catalyst, H2O2 concentration and their interaction were significant factors (p < 0.05) in the elimination of the microorganisms. Thus, under the best conditions (3.4 mg L-1 of iron (III) oxide and 10 mg L-1 of H2O2) in the experimental ranges, complete inactivation of E. coli and S. typhimurium was achieved (6-log reduction) in 120 min using the photo-Fenton treatment with both iron-oxide phases. Furthermore, the photocatalytic elimination of both bacteria by the photo-Fenton process using hematite and maghemite in secondary-treated wastewater effluent was performed obtaining slower inactivation rates (1.2-5.9 times) than in distilled water due to the matrix effect of the effluent from a wastewater treatment plant. Nevertheless, the process continued to be effective in the effluent, achieving complete bacterial elimination in 150 min using the hematite phase. Additionally, the SEM images of the bacterial cells showed that the heterogeneous photo-Fenton treatment generated permanent and irreversible cell damage, resulting in complete cell death.

Magnetic porous carbons derived from cobalt(ii)-based metal-organic frameworks for the solid-phase extraction of sulfonamides.

In this work, the dispersive solid-phase extraction of sulfonamide antibiotics was evaluated using magnetic porous carbons derived from cobalt(ii)-based metal-organic frameworks. By direct carbonization under the inert atmosphere of Co-SIM-1, Co-MOF-74 and Co-DABCO MOFs, different magnetic porous carbons were prepared and characterized to study their structural, morphological, chemical and textural properties. Their performance for the simultaneous extraction of three sulfonamides (sulfadiazine, sulfamerazine and sulfamethazine), prior to HPLC analysis, was also evaluated, obtaining the best results (>95%) in the case of C/Co-SIM-1 carbon, probably due to its bimodal pore structure, high surface area and large amount of surface defects. Using this adsorbent, the effect of the solution pH and contact time on the adsorption of the sulfonamides, and the reusability of the carbon were studied.

Experimental data on the production and characterization of biochars derived from coconut-shell wastes obtained from the Colombian Pacific Coast at low temperature pyrolysis.

Biochars are emerging eco-friendly products showing outstanding properties in areas such as carbon sequestration, soil amendment, bioremediation, biocomposites, and bioenergy. These interesting materials can be synthesized from a wide variety of waste-derived sources, including lignocellulosic biomass wastes, manure and sewage sludge. In this work, abundant data on biochars produced from coconut-shell wastes obtained from the Colombian Pacific Coast are presented. Biochar synthesis was performed varying the temperature (in the range: 280 °C-420 °C) and O2 feeding (in the range: 0-5% v/v) in the pyrolysis reaction. Production yields and some biochar properties such as particle size, Zeta Potential, elemental content (C, N, Al, B, Ca, Cu, Fe, K, Li, Mg, Mn, Na, P, S, Ti, Zn), BET surface area, FT-IR spectrum, XRD spectrum, and SEM morphology are presented. This data set is a comprehensive resource to gain a further understanding of biochars, and is a valuable tool for addressing the strategic exploitation of the multiple benefits they have.

Photo-assisted electrochemical degradation of polychlorinated biphenyls with boron-doped diamond electrodes.

The capacity of the photo electro-Fenton (PEF) process to degrade a mixture of seven polychlorinated biphenyl (PCB) congeners was studied. Boron-doped diamond (BDD) sheets were used as anode and cathode in the experimental electrolytic cell that contained Na2SO4 0.05 M at pH 3 as supporting electrolyte for the electro generation of H2O2 at the cathode. The effects of UV light intensity (254 and 365 nm), current density (8, 16 and 24 mA cm-2) and ferrous ion dosage (0.1, 0.2 and 0.3 mM) on PCB (C0 = 50 µg L-1) degradation were evaluated. The highest level of PCB degradation (97%) was achieved with 16 mA cm-2 of current density, 0.1 mM of ferrous ion and UV light at 365 nm as irradiation source after 6 h of reaction. PCB28, PCB52 and PCB101 were not detected after 0.5, 1.5 and 3 h of reaction, respectively. The degradation of PCB138, PCB153, PCB180 and PCB209 was also high (>95%). The PEF system outperformed other oxidation processes (electro-Fenton, anodic oxidation, Fenton, photo-Fenton and UV photolysis) in terms of reaction rate and degradation efficiency. These results demonstrate for the first time the degradation of PCB209, the most highly chlorinated PCB congener, by an advanced electrochemical oxidation process.

Degradation of anti-inflammatory drugs in municipal wastewater by heterogeneous photocatalysis and electro-Fenton process.

Non-steroidal anti-inflammatory drugs (NSAID) are compounds frequently found in municipal wastewater and their degradation by conventional wastewater treatment plants (WWTP) is generally incomplete. This study compared the efficiency of two advanced oxidation processes (AOP), namely heterogeneous photocatalysis (HP) and electro-Fenton (EF), in the degradation of a mixture of common NSAID (diclofenac, ibuprofen and naproxen) dissolved in either deionized water or effluent from a WWTP. Both processes were effective in degrading the NSAID mixture and the trend of degradation was as follows, diclofenac > naproxen > ibuprofen. EF with a current density of 40 mA cm-2 and 0.3 mmol Fe2+ L-1 was the most efficient process to mineralize the organic compounds, achieving up to 92% TOC removal in deionized water and 90% in the WWTP effluent after 3 h of reaction. HP with 1.4 g TiO2 L-1 at pH 7 under sunlight, produced 85% TOC removal in deionized water and 39% in WWTP effluent also after 3 h treatment. The lower TOC removal efficiency shown by HP with the WWTP effluent was attributed mainly to the scavenging of reactive species by background organic matter in the wastewater. On the contrary, inorganic ions in the wastewater may produce oxidazing species during the EF process, which contributes to a higher degradation efficiency. EF is a promising option for the treatment of anti-inflammatory pharmaceuticals in municipal WWTP at competitive electrical energy efficiencies.

Performance of Bi2O3/TiO2 prepared by sol-gel on p-Cresol degradation under solar and visible light.

Photocatalytic degradation of p-Cresol was evaluated using the mixed oxide Bi2O3/TiO2 (containing 2 and 20% wt. Bi2O3 referred as TB2 and TB20) and was compared with bare TiO2 under simulated solar radiation. Materials were prepared by the classic sol-gel method. All solids exhibited the anatase phase by X-ray diffraction (XRD) and Raman spectroscopy. The synthesized materials presented lower crystallite size and Eg value, and also higher surface area as Bi2O3 amount was increased. Bi content was quantified showing near to 70% of theoretical values in TB2 and TB20. Bi2O3 incorporation also was demonstrated by X-ray photoelectron spectroscopy (XPS). Characterization of mixed oxides suggests a homogeneous distribution of Bi2O3 on TiO2 surface. Photocatalytic tests were carried out using a catalyst loading of 1 g L-1 under simulated solar light and visible light. The incorporation of Bi2O3 in TiO2 improved the photocatalytic properties of the synthesized materials obtaining better results with TB20 than the unmodified TiO2 under both radiation sources.

Synthesis of Cr3+-doped TiO2 nanoparticles: characterization and evaluation of their visible photocatalytic performance and stability.

Cr3+-doped TiO2 nanoparticles (Ti-Cr) were synthesized by microwave-assisted sol-gel method. The Ti-Cr catalyst was characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, N2 adsorption-desorption analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy (XPS) and zetametry. The anatase mesoporous Ti-Cr material exhibited a specific surface area of 54.5 m2/g. XPS analysis confirmed the proper substitution of Ti4+ cations by Cr3+ cations in the TiO2 matrix. The particle size was of average size of 17 nm for the undoped TiO2 but only 9.5 nm for Ti-Cr. The Cr atoms promoted the formation of hydroxyl radicals and modified the surface adsorptive properties of TiO2 due to the increase in surface acidity of the material. The photocatalytic evaluation demonstrated that the Ti-Cr catalyst completely degraded (4-chloro-2-methylphenoxy) acetic acid under visible light irradiation, while undoped TiO2 and P25 allowed 45.7% and 31.1%, respectively. The rate of degradation remained 52% after three cycles of catalyst reuse. The higher visible light photocatalytic activity of Ti-Cr was attributed to the beneficial effect of Cr3+ ions on the TiO2 surface creating defects within the TiO2 crystal lattice, which can act as charge-trapping sites, reducing the electron-hole recombination process.

Automated on-line monitoring of the TiO2-based photocatalytic degradation of dimethyl phthalate and diethyl phthalate.

A fully automated on-line system for monitoring the TiO2-based photocatalytic degradation of dimethyl phthalate (DMP) and diethyl phthalate (DEP) using sequential injection analysis (SIA) coupled to liquid chromatography (LC) with UV detection was proposed. The effects of the type of catalyst (sol-gel, Degussa P25 and Hombikat), the amount of catalyst (0.5, 1.0 and 1.5 g L-1), and the solution pH (4, 7 and 10) were evaluated through a three-level fractional factorial design (FFD) to verify the influence of the factors on the response variable (degradation efficiency, %). As a result of FFD evaluation, the main factor that influences the process is the type of catalyst. Degradation percentages close to 100% under UV-vis radiation were reached using the two commercial TiO2 materials, which present mixed phases (anatase/rutile), Degussa P25 (82%/18%) and Hombikat (76%/24%). 60% degradation was obtained using the laboratory-made pure anatase crystalline TiO2 phase. The pH and amount of catalyst showed minimum significant effect on the degradation efficiencies of DMP and DEP. Greater degradation efficiency was achieved using Degussa P25 at pH 10 with 1.5 g L-1 catalyst dosage. Under these conditions, complete degradation and 92% mineralization were achieved after 300 min of reaction. Additionally, a drastic decrease in the concentration of BOD5 and COD was observed, which results in significant enhancement of their biodegradability obtaining a BOD5/COD index of 0.66 after the photocatalytic treatment. The main intermediate products found were dimethyl 4-hydroxyphthalate, 4-hydroxy-diethyl phthalate, phthalic acid and phthalic anhydride indicating that the photocatalytic degradation pathway involved the hydrolysis reaction of the aliphatic chain and hydroxylation of the aromatic ring, obtaining products with lower toxicity than the initial molecules.

Optimization of solid-phase extraction of parabens and benzophenones in water samples using a combination of Plakett-Burman and Box-Behnken designs.

An automated method for the analysis of methylparaben, propylparaben, benzophenone-3, and benzophenone-4 in water effluents via on-line solid-phase extraction coupled with high-performance liquid chromatography/ultraviolet detection was proposed. The preconcentration parameters were studied using Plackett-Burman and Box-Behnken experimental designs using a C18 sorbent material. The results demonstrated that the eluent volume, composition, and sorbent amount were statistically significant. Optimal conditions for these variables were an eluent volume of 1.55 mL, eluent composition of acetonitrile 100% v/v, and sorbent amount of 100 mg. The eluted sample was analyzed on-line using high-performance liquid chromatography equipped with a reversed-phase C18 column and ultraviolet detection. Separation of the analytes was achieved in 15 min using gradient elution with acetonitrile/water. A simple, sensitive, and rapid analytical method was proposed for personal care compounds without sophisticated or expensive equipment. The limits of detection were 1.20, 1.73, 2.51, and 4.67 µg/L for propylparaben, methylparaben, benzophenone-3, and benzophenone-4, respectively. The analysis time was 48 min, consuming only 1.59 mL of eluent acetonitrile for the solid phase extraction step, with minimal sample handling. The method was applied to the analysis of spiked swimming pool and wastewater, with recoveries between 65-107%. These results indicate the reliability of the flow-based procedure.

Advanced oxidation of real sulfamethoxazole + trimethoprim formulations using different anodes and electrolytes.

A commercial sulfamethoxazole + trimethoprim formulation has been degraded in 0.050 M Na2SO4 at pH 3.0 by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF), photoelectro-Fenton with a 6-W UVA lamp (PEF) and solar photoelectro-Fenton (SPEF). The tests were performed in an undivided cell with an IrO2-based, Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 electrogeneration. The anode material had little effect on the accumulated H2O2 concentration. Both drugs always obeyed a pseudo-first-order decay with low apparent rate constant in EO-H2O2. Much higher values were found in EF, PEF and SPEF, showing no difference because the main oxidant was always OH formed from Fenton's reaction between H2O2 and added Fe2+. The solution mineralization increased in the sequence EO-H2O2 < EF < PEF < SPEF regardless of the anode. The IrO2-based and Pt anodes behaved similarly but BDD was always more powerful. In SPEF, similar mineralization profiles were found for all anodes because of the rapid removal of photoactive intermediates by sunlight. About 87% mineralization was obtained as maximum for the powerful SPEF with BDD anode. Addition of Cl- enhanced the decay of both drugs due to their quicker reaction with generated active chlorine, but the formation of persistent chloroderivatives decelerated the mineralization process. Final carboxylic acids like oxalic and oxamic were detected, yielding Fe(III) complexes that remained stable in EF with BDD but were rapidly photolyzed in SPEF with BDD, explaining its superior mineralization ability.

Determination of phthalates in bottled water by automated on-line solid phase extraction coupled to liquid chromatography with uv detection.

An on-line solid phase extraction coupled to liquid chromatography with UV detection (SPE/LC-UV) method was automated by the multisyringe flow-injection analysis (MSFIA) system for the determination of three phthalic acid esters (PAEs). The PAEs determined in drinking water stored in polyethylene terephthalate (PET) bottles of ten commercial brands were dimethyl phthalate (DMP), diethyl phthalate (DEP) and dibutyl phthalate (DBP). C18-bonded silica membrane was used for isolation and enrichment of the PAEs in water samples. The calibration range of the SPE/LC-UV method was 2.5-100µgL-1 for DMP and DEP and 10-100µgL-1 for DBP with correlation coefficients (r) ranging from 0.9970 to 0.9975. Limits of detection (LODs) were between 0.7 and 2.4µgL-1. Inter-day reproducibility performed at two concentration levels (10 and 100µgL-1) expressed as relative standard deviation (%RSD) were found in the range of 0.9-4.0%. The solvent volume was reduced to 18mL with a total analysis time of 48min per sample. The major species detected in bottled water samples was DBP reaching concentrations between 20.5 and 82.8µgL-1. The recovery percentages for the three analytes in drinking water were 80-115%. The migration test showed a great variation in the sum of migrated PAEs level (10.2-50.6µgL-1) among the PET bottle brands analyzed indicating that the presence of these contaminants in the plastic containers may depend on raw materials and the conditions used during their production process.

An evaluation of the bioaccessibility of arsenic in corn and rice samples based on cloud point extraction and hydride generation coupled to atomic fluorescence spectrometry.

A simple, inexpensive and rapid method was proposed for the determination of bioaccessible arsenic in corn and rice samples using an in vitro bioaccessibility assay. The method was based on the preconcentration of arsenic by cloud point extraction (CPE) using o,o-diethyldithiophosphate (DDTP) complex, which was generated from an in vitro extract using polyethylene glycol tert-octylphenyl ether (Triton X-114) as a surfactant prior to its detection by atomic fluorescence spectrometry with a hydride generation system (HG-AFS). The CPE method was optimized by a multivariate approach (two-level full factorial and Doehlert designs). A photo-oxidation step of the organic species prior to HG-AFS detection was included for the accurate quantification of the total As. The limit of detection was 1.34µgkg(-1) and 1.90µgkg(-1) for rice and corn samples, respectively. The accuracy of the method was confirmed by analyzing certified reference material ERM BC-211 (rice powder). The corn and rice samples that were analyzed showed a high bioaccessible arsenic content (72-88% and 54-96%, respectively), indicating a potential human health risk.

Salicylic acid degradation by advanced oxidation processes. Coupling of solar photoelectro-Fenton and solar heterogeneous photocatalysis.

A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a photocatalytic photoreactor filled with TiO2-coated glass spheres has been utilized to couple solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165mgL(-1) salicylic acid solution of pH 3.0. Organics were destroyed by OH radicals formed on the TiO2 photocatalyst and at the Pt anode during water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and cathodically generated H2O2, along with the photolytic action of sunlight. Poor salicylic acid removal and mineralization were attained using SPC, anodic oxidation with electrogenerated H2O2 (AO-H2O2) and coupled AO-H2O2-SPC. The electro-Fenton process accelerated the substrate decay, but with low mineralization by the formation of byproducts that are hardly destroyed by OH. The mineralization was strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled SPEF-SPC due to the additional oxidation by OH at the TiO2 surface. The effect of current density on the performance of both processes was examined. The most potent SPEF-SPC process at 150mAcm(-2) yielded 87% mineralization and 13% current efficiency after consuming 6.0AhL(-1). Maleic, fumaric and oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC.

Coupling of solar photoelectro-Fenton with a BDD anode and solar heterogeneous photocatalysis for the mineralization of the herbicide atrazine.

Here, the synergetic effect of coupling solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) on the mineralization of 200mL of a 20mg L(-1) atrazine solution, prepared from the commercial herbicide Gesaprim, at pH 3.0 was studied. Uniform, homogeneous and adherent anatase-TiO2 films onto glass spheres of 5mm diameter were prepared by the sol-gel dip-coating method and used as catalyst for SPC. However, this procedure yielded a poor removal of the substrate because of the low oxidation ability of positive holes and OH formed at the catalyst surface to destroy it. Atrazine decay was improved using anodic oxidation (AO), electro-Fenton (EF), SPEF and coupled SPEF-SPC at 100mA. The electrolytic cell contained a boron-doped diamond (BDD) anode and H2O2 was generated at a BDD cathode fed with an air flow. The removal and mineralization of atrazine increased when more oxidizing agents were generated in the sequence AO

Low Concentration Fe-Doped Alumina Catalysts Using Sol-Gel and Impregnation Methods: The Synthesis, Characterization and Catalytic Performance during the Combustion of Trichloroethylene.

The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al2O3 phase formed and to correlate the catalytic properties during trichloroethylene (TCE) combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al2O3 surface. The X-ray photoelectron spectra (XPS), FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al2O3 lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%.

On-line monitoring of the photocatalytic degradation of 2,4-D and dicamba using a solid-phase extraction-multisyringe flow injection system.

A fully automated on-line system for monitoring the photocatalytic degradation of herbicides was developed using multisyringe flow injection analysis (MSFIA) coupled to a solid phase extraction (SPE) unit with UV detection. The calibration curves were linear in the concentration range of 100-1000 µg L(-1) for 3,6-dichloro-2-methoxybenzoic acid (dicamba) and 500-3000 µg L(-1) for 2,4-dichlorophenoxyacetic acid (2,4-D), while the detection limits were 30 and 135 µg L(-1) for dicamba and 2,4-D, respectively. The monitoring of the photocatalytic degradation (TiO2 anatase/UV 254 nm) of these two herbicides was performed by MSFIA-SPE system using a small sample volume (2 mL) in a fully automated approach. The degradation was assessed in ultrapure and drinking water with initial concentrations of 1000 and 2000 µg L(-1) for dicamba and 2,4-D, respectively. Degradation percentages of approximately 85% were obtained for both herbicides in ultrapure water after 45 min of photocatalytic treatment. A similar degradation efficiency in drinking water was observed for 2,4-D, whereas dicamba exhibited a lower degradation percentage (75%), which could be attributed to the presence of inorganic species in this kind of water.

Photocatalytical removal of inorganic and organic arsenic species from aqueous solution using zinc oxide semiconductor.

The photocatalytic removal of arsenite [As(III)] and monomethylarsonic acid [MMA(V)] was investigated in the presence of UV light (350 nm) and aqueous suspensions of ZnO synthesized by the sol-gel technique. Photocatalytic removal of these potent arsenic compounds results in the effective and rapid mineralization to less toxic inorganic arsenate [As(V)]. The effect of ZnO loading and solution pH on the treatment efficiency of the UV/ZnO photocatalytic process was evaluated. The optimal conditions for the removal of 5 mg L(-1) [As(III)] and [MMA(V)] aqueous solutions were observed at catalyst loadings of 0.25 and 0.50 g L(-1) with solution pH values of 7 and 8, respectively. Under these conditions, the activity of photocatalyst sol-gel ZnO was compared with TiO2 Degussa P25 and commercial ZnO catalyst. The results demonstrate that the high adsorption capacity of ZnO synthesized by sol-gel gives enhanced removal of arsenic species from water samples, indicating that this catalyst is a promising material for treatment of arsenic contaminated groundwater.

Mineralization of Acid Yellow 36 azo dye by electro-Fenton and solar photoelectro-Fenton processes with a boron-doped diamond anode.

The degradation of the Acid Yellow 36 (AY36) azo dye is studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF) using a recirculation flow plant with an undivided cell containing a boron-doped diamond anode and an air-diffusion cathode for H2O2 electrogeneration, coupled with a solar photoreactor. A solution of 2.5L with 108 mg L⁻¹ of the dye and 0.5 mM Fe²(+) at pH 3.0 was comparatively treated at constant current. Hydroxyl radicals formed from Fenton's reaction and at the anode surface are the main oxidants. Total mineralization is almost achieved in SPEF, while EF yields poor TOC removal. Both processes are accelerated with increasing current. AY36 decays with similar rate in EF and SPEF following a pseudo first-order reaction, but the solution is more slowly decolorized because of the formation of conjugated byproducts. NH4(+) ion is released in SPEF, while NO3⁻ ion is mainly lost in EF. Tartronic, maleic, fumaric, oxalic, formic and oxamic acids are detected as generated carboxylic acids. Fe(III)-oxalate complexes are largely accumulated in EF and their quick photodecomposition in SPEF explains its higher oxidation power. The SPEF method yields greater current efficiency and lower energy cost as current decreases, and then it is more viable at low currents.

Performance of the photo-Fenton process in the degradation of a model azo dye mixture.

The degradation of a model mixture composed of Acid Yellow 36 (AY36) and Methyl Orange (MO) azo dyes was performed using the photo-Fenton process (PFP). The performance of this process conducted under artificial UV light (365 nm) was compared with the Fenton reaction. Some important operating parameters that affect the degradation of azo dyes, such as initial Fe(2+) and H(2)O(2) concentrations and the presence or absence of chloride ions, were investigated. Decolorisation of the dye mixture sample was achieved in 70 min with the photo-Fenton reaction, while the complete mineralization evaluated by TOC abatement was completed in 180 min. These results provide important knowledge for the treatment of wastewater containing azo dye mixtures by Fenton and photo-Fenton oxidation processes.