Palladium-modified TiO2 films in a photocatalytic microreactor: evaluation of radiation absorption properties and pollutant degradation efficiency.

Pure (TiO2) and 0.1 nominal atomic percent of palladium-modified TiO2 (Pd-TiO2) films were synthesized via a sol-gel method and compared through their physicochemical properties and photocatalytic activity in the degradation of an emerging contaminant, 17-α-ethinylestradiol (EE2). The activity of the films was studied using a continuous flow, planar microreactor under simulated sunlight. Catalysts characterization included X-ray diffraction, UV-Visible diffuse reflectance and transmittance spectroscopy, atomic force microscopy, transmission electron microscopy, Raman spectroscopy, N2 physisorption analysis, and X-ray photoelectron spectroscopy. The modification of TiO2 with palladium confined the size of anatase phase crystallites, increased the specific surface area and improved radiation absorption. PdO domains on TiO2 were observed. In all the tested conditions, higher conversion of EE2 was achieved with the Pd-TiO2 film compared with the TiO2 film, presenting an 80% increase in the reaction rate. The performance of the catalytic films was also assessed by the calculation of two efficiency parameters: radiation absorption efficiency and quantum efficiency of reaction. The Pd-TiO2 film showed a notable enhancement of the absorption of the incident radiation and a more efficient utilization of the absorbed photons to degrade the target pollutant.

Effects of organic matter addition on chronically hydrocarbon-contaminated soil.

Soil is the recipient of organic pollutants as a consequence of anthropogenic activities. Hydrocarbons are contaminants that pose a risk to human and environmental health. Bioremediation of aging contaminated soils is a challenge due to the low biodegradability of contaminants as a result of their interaction with the soil matrix. The aim of this work was to evaluate the effect of both composting and the addition of mature compost on a soil chronically contaminated with hydrocarbons, focusing mainly on the recovery of soil functions and transformations of the soil matrix as well as microbial community shifts. The initial pollution level was 214 ppm of polycyclic aromatic hydrocarbons (PAHs) and 2500 ppm of aliphatic hydrocarbons (AHs). Composting and compost addition produced changes on soil matrix that promoted the release of PAHs (5.7 and 15 % respectively) but not the net PAH elimination. Interestingly, composting stimulated AHs elimination (about 24 %). The lack of PAHs elimination could be attributed to the insufficient PAHs content to stimulate the microbial degrading capacity, and the preferential consumption of easily absorbed C sources by the bacterial community. Despite the low PAH catabolic potential of the aging soil, metabolic shift was driven by the addition of organic matter, which could be monitored by the ratio of Proteobacteria to Actinobacteria combined with E4/E6 ratio. Regarding the quality of the soil, the nutrients provided by the exogenous organic matter contributed to the recovery of the global functions and species diversity of the soil along with the reduction of phytotoxicity.

Co-treatment of an oily sludge and aged contaminated soil: permanganate oxidation followed by bioremediation.

The bioremediation of an oily sludge (321 ± 30 mg of polycyclic aromatic hydrocarbons/kgDRY SLUDGE and 13420 ± 1300 mg of aliphatic hydrocarbons/kgDRY SLUDGE) by mixture with contaminated soil (23 ± 2 mg of polycyclic aromatic hydrocarbons/kgDRY SOIL and 98 ± 10 mg of aliphatic hydrocarbons/kgDRY SOIL) was studied. Furthermore, the effect of oxidative pretreatments (persulfate and permanganate) on the performance of the global process was examined. The treatments reached contamination levels lower than the original residues, indicating the presence of synergic processes between a highly contaminated sludge and soil with a selected hydrocarbon-degrading community. Pretreatment with permanganate significantly improved biodegradation, possibly due to the increase in bioavailability and biodegradability of petroleum hydrocarbons. Two months of incubation was enough to reach the complete elimination of polycyclic aromatic hydrocarbons and 92% elimination of aliphatic hydrocarbons. Monitoring using five parameters (concentration of total petroleum hydrocarbons, total cultivable heterotrophic bacteria count, lipase and dehydrogenase activities, and polycyclic aromatic hydrocarbon-degrading bacteria count) as an approach for a preliminary scanning of the effectiveness of a treatment is proposed based on principal components analysis.

Strategies for oxidation of PAHs in aged contaminated soil by batch reactors.

Polycyclic aromatic hydrocarbons (PAH) are neutral, nonpolar and hydrophobic molecules that tend to sorb onto soil organic matter. Chemical oxidation is a good choice to avoid the limitations of bioremediation. To evaluate the efficiency of different types of oxidation (permanganate, hydrogen peroxide, and persulfate) and activation (heat, alkaline, and iron), batch reactors were prepared. The soil was contaminated with phenanthrene and pyrene (1200 ± 200 and 2800 ± 100mg per kg of dry soil, respectively) and aged for fifteen months. Treatments were prepared with 10g of contaminated dry soil and 20ml of water and incubated at room temperature for 7 days. Analyses of phenanthrene and pyrene concentrations, soil pH and electric conductivity were performed. Counts of heterotrophic cultivable bacteria on R2A medium and PAH-degraders were carried out after 7 days of treatment. The persulfate treatment at room temperature, without the addition of activators, achieved better results than treatments with the same doses of permanganate or hydrogen peroxide. All the strategies to improve persulfate treatments yielded higher degradation of pyrene than the biological control, as expected from the structural description of this compound by Clar's model. The thermal activation of persulfate (65°C for 6h) led to the degradation of more than 90% of both PAHs after 7 days of treatment.

Degradation of carbamazepine in surface water: performance of Pd-modified TiO2 and Ce-modified ZnO as photocatalysts.

Carbamazepine is a widely used antiepileptic drug to control and treat a variety of disorders that is frequently detected in surface water, and in municipal and urban wastewater. This recalcitrant pollutant could be removed by alternative advanced oxidation technology such as heterogeneous photocatalysis. Ce-modified ZnO and Pd-modified TiO2 were synthesized by a microwave-assisted sol-gel method. According to the characterizations (Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy), a mixture of oxides was determined in both materials: CeO2/ZnO and PdO/TiO2. Photocatalytic degradation of carbamazepine in pure water under visible light (3 h) was assayed. The degradation percentage obtained with each catalyst was 80%, 53%, 20%, and 9% for ZnO, Ce-modified ZnO, TiO2, and Pd-modified TiO2, respectively. The leaching of Zn as a possible source of water contamination was tested, finding the lowest value for Ce-modified ZnO by adjusting the initial pH up to neutrality. Later, an environmentally relevant concentration of carbamazepine (228 µg L-1) was assayed, using local surface water (pH = 8.3). Despite the presence of other compounds in the real water matrix, after 5 h of photocatalysis, a 56% of degradation of the pharmaceutical and low leaching of Zn were achieved. The use of Ce-modified ZnO activated by visible light is a promising strategy for the abatement of pharmaceutical active compounds.

V-doped TiO2 photocatalysts and their application to pollutant degradation.

V-doped TiO2 materials (0.01, 0.05, 0.10, and 1.00 nominal atomic %) were synthesized by the sol-gel method and characterized by X-ray diffraction, Raman spectroscopy, UV-visible diffuse reflectance spectroscopy, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and H2-temperature programmed reduction. Two vanadium precursors (vanadyl acetylacetonate and ammonium metavanadate) and three calcination temperatures (400, 500, and 600 °C, with and without air circulation) were assayed. The efficiency of the materials as photocatalysts was studied by the degradation of phenol with UV and visible lamps. The photocatalyst prepared from vanadium acetylacetonate, with a vanadium content of 0.01 nominal atomic %, calcination at 400 °C without air circulation (0.01VTi-400), showed the best performance, reaching 100% and 30% degradation of phenol (50 µM) by irradiation with UV lamps (3 h) and visible lamps (5 h), respectively. To evaluate the efficiency of this catalyst in the degradation of other structurally related compounds, two substituted phenols were selected: 4-chlorophenol and 4-nitrophenol. The 0.01VTi-400 photocatalyst showed to be applicable to the degradation of phenolic compounds when the substituent was an activating group or a weakly deactivating group (for electrophilic reactions). Additionally, the selectivity of 0.01VTi-400 for phenol degradation in the presence of Aldrich humic acid was tested: phenol degradation reached 68% (3 h, UV lamps). The performance of 0.01VTi-400 indicated that it is a promising material for further applications.

Identification of an intermediate for 1,8-dihydroxynaphthalene-melanin synthesis in a race-2 isolate of Fulvia fulva (syn. Cladosporium fulvum).

Fulvia fulva (syn. Cladosporium fulvum, Mycosphaerellaceae) is a dematiaceous fungus that causes tomato leaf mould. It is characterized by its biotrophic lifestyle and the synthesis of the bianthraquinone secondary metabolite, cladofulvin. The aim of the study was to characterize the dark pigment photochemically synthesized by F. fulva and to elucidate its biochemical pathway. We isolated a black pigment from in vitro cultures of the fungus. We determined the pigment to be 1,8-dihydroxynaphthalene (DHN)-melanin based on its chemical and photochemical characteristics, as well as the presence of flaviolin, when fungal reductases were inhibited by tricyclazole. Furthermore, the pks1 gene involved in pigment synthesis has a KS domain already associated with DHN-melanin. Our findings support the relevance of studying melanization in F. fulva.

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol.

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.

Combination of sunlight, oxidants, and Ce-doped TiO2 for phenol degradation.

The degradation of phenol was used as a model reaction to investigate the photocatalytic properties of cerium-doped (0.1 nominal atomic percent) TiO2 catalysts in the presence and in the absence of oxidants: persulfate (PS) or hydrogen peroxide (HP). Experiments were performed in batch reactors using either artificial light (ultraviolet or visible) or solar exposure during spring-summer seasons in La Plata City (34.90° S, 57.92° W, 15 MASL). The formation of hydroquinone, catechol, and p-benzoquinone was observed in all the experiments. Additionally, for the experiments with PS (with or without catalyst), evidence of the formation of dimers and trimers was found. Total degradation of phenol (250 µM) was achieved with doped material and 7 mM of PS (two doses) after 3 h of solar exposure (H SUV, T = 2.9 ± 0.6 105 J m-2).

The influence of Ce doping of titania on the photodegradation of phenol.

Pure and cerium-doped [0.05, 0.1, 0.3, 0.5, and 1.0 Ce nominal atomic % (at.%)] TiO2 was synthesized by the sol-gel method. The obtained catalysts were characterized by X-ray diffraction (XRD), UV-visible diffused reflectance spectroscopy (DRS), Raman, and BET surface area measurement. The photocatalytic activity of synthesized samples for the oxidative degradation of phenol in aqueous suspension was investigated. The content of Ce in the catalysts increases both the transition temperature for anatase to rutile phase transformation and the specific surface area, and decreases the crystallite size of anatase phase, the crystallinity, and the band gap energy value. The material with higher efficiency corresponds to 0.1 Ce nominal at.%. Under irradiation with 350 nm lamps, the degradation of phenol could be described as an exponential trend, with an apparent rate constant of (9.1 ± 0.6) 10(-3) s(-1) (r(2) = 0.98). Hydroquinone was identified as the main intermediate.

Remediation of phenanthrene-contaminated soil by simultaneous persulfate chemical oxidation and biodegradation processes.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds with carcinogenic and/or mutagenic potential. To address the limitations of individual remediation techniques and to achieve better PAH removal efficiencies, the combination of chemical and biological treatments can be used. The degradation of phenanthrene (chosen as a model of PAH) by persulfate in freshly contaminated soil microcosms was studied to assess its impact on the biodegradation process and on soil properties. Soil microcosms contaminated with 140 mg/kgDRY SOIL of phenanthrene were treated with different persulfate (PS) concentrations 0.86-41.7 g/kgDRY SOIL and incubated for 28 days. Analyses of phenanthrene and persulfate concentrations and soil pH were performed. Cultivable heterotrophic bacterial count was carried out after 28 days of treatment. Genetic diversity analysis of the soil microcosm bacterial community was performed by PCR amplification of bacterial 16S rDNA fragments followed by denaturing gradient gel electrophoresis (DGGE). The addition of PS in low concentrations could be an interesting biostimulatory strategy that managed to shorten the lag phase of the phenanthrene biological elimination, without negative effects on the physicochemical and biological soil properties, improving the remediation treatment.

Chloride anion effect on the advanced oxidation processes of methidathion and dimethoate: role of Cl2(·-) radical.

The reaction of phosphor-containing pesticides such as methidathion (MT) and dimethoate (DM) with dichloride radical anions (Cl(2)(·-)) was investigated. The second order rate constants (1.3 ± 0.4) × 10(8) and (1.1 ± 0.4) × 10(8) M(-1) s(-1) were determined for the reaction of Cl(2)(·-) with MT and DM, respectively. A reaction mechanism involving an initial charge transfer from the sulfide groups of the insecticides to Cl(2)(·-) is proposed and supported by the identified transient intermediates and reaction products. The formation of chlorinated byproducts was determined. The unexpected consequences of an efficient Cl(2)(·-) reactivity towards MT and DM on the degradation capacity by Advanced Oxidation Procedures applied to polluted waters containing the insecticides and Cl(-) anions is discussed.

Phenol depletion by thermally activated peroxydisulfate at 70°C.

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70°C from contaminated waters is investigated. Phenol in concentrations of 10(-4) to 5×10(-4)M is quantitatively depleted by 5×10(-3) to 10(-2)M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70°C does not lead to the mineralization of phenol. Thus PS activation at 70°C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.

Degradation of the herbicides clomazone, paraquat, and glyphosate by thermally activated peroxydisulfate.

Activated sodium peroxydisulfate has the potential to in situ destruct many organic contaminants because of the generation of the stronger oxidant sulfate radical. From photochemical activation of peroxydisulfate in flash-photolysis experiments, the bimolecular rate constants for the reaction of sulfate radical with glyphosate (1.6 × 10(8) M(-1) s(-1)) and paraquat (1.2 × 10(9) M(-1) s(-1)) at 25 °C were obtained. Thermal activation of peroxydisulfate was shown to degrade the herbicides clomazone, paraquat, and glyphosate. Although the herbicide degradation was observed to take place in less than 1 h, the mineralization of the organic carbon required longer reaction times, because of the formation of stable organic intermediates. For similar initial total organic carbon (TOC) values, TOC profiles were similar for experiments with different substrates (the herbicides, humic acids, and a mixture of glyphosate and humic acids), which indicates that the mineralization of all of the samples is limited by the production of SO(4)(•) (-) radicals. A linear correlation between the initial amount of SO(4)(•) (-) needed per mole of C and the average oxidation state was found.

Generation of chemisorbed benzyl radicals on silica nanoparticles.

Functionalized silica nanoparticles (NP) were obtained by esterification of the silanol groups of fumed silica nanoparticles with benzyl alcohol. These particles were characterized by Fourier transform infrared spectroscopy, (13)C and (29)Si NMR spectroscopy, thermogravimetry, total organic carbon, Brunauer-Emmett-Teller analysis, UV-visible spectroscopy, and transmission electron microscopy. NP suspensions in water/acetonitrile mixtures were used as quenchers of benzophenone (BP) phosphorescence in time-resolved experiments at the excitation wavelength of 266 nm. The phosphorescence signals obtained in the presence of the nanoparticles were fitted to biexponential decays. Both decays were accelerated in the presence of increasing amounts of NP. A model, including the reversible adsorption of BP on the NP, which was supported by computer simulations accounts for the observed results. Laser flash-photolysis experiments with excitation at 266 nm of NP suspensions in water/acetonitrile in the presence of BP generated benzyl radicals that were attached to the silica surface. These radicals were detected at their absorption maxima (320 nm) by transient optical techniques.

Alloxan-dialuric acid cycling: a complex redox mechanism.

Time-resolved kinetic studies involving the reactions of alloxan (A.H(2)O) with the reducing species superoxide and carbon dioxide radical anions and the reaction of dialuric acid (HA(-)) with sulphate radicals showed that the same radical (AH(.)) was formed either by the one-electron reduction of alloxan or by the one-electron oxidation of dialuric acid. A mechanism including several reversible reactions was proposed and validated. A detailed kinetic analysis yields the following bimolecular rate constants: k(A.H(2)O + [image omitted] ) < 10(5) m ( -1 ) s(-1), k(A.H(2)O + O(2) (-))=(3.4+/-0.5)x10(6) m ( -1 ) s(-1), k(HA(-)+[image omitted] )=(8+/-1)x10(7) m ( -1 ) s(-1) and k(AH(.)+AH(.))=(1.7+/-0.8)x10(8) m ( -1 ) s(-1). From these values, the redox potentials E degrees (A.H(2)O,H(+)/AH(.))=(-290+/-20) mV, E degrees (AH(.)/HA(-))=(277+/-20) mV and E degrees (A.H(2)O,H(+)/HA(-))=(-15+/-20) mV, were obtained.

Thermally activated peroxydisulfate in the presence of additives: a clean method for the degradation of pollutants.

The kinetics and mechanism of the thermal activation of peroxydisulfate, in the temperature range from 60 to 80 degrees C, was investigated in the presence and absence of sodium formate as an additive to turn the oxidizing capacity of the reaction mixture into a reductive one. Trichloroacetic acid, TCA, whose degradation by a reductive mechanism is well reported in the literature, was used as a probe. The chemistry of thermally activated peroxydisulfate is described by a reaction scheme involving free radical generation. The proposed mechanism is evaluated by a computer simulation of the concentration profiles obtained under different experimental conditions. In the presence of formate, SO(4)(-) radicals yield CO(2)(-), which are the main species available for degrading TCA. Under the latter conditions, TCA is more efficiently depleted than in the absence of formate, but otherwise identical conditions of temperature and [S(2)O(8)(2-)]. We therefore conclude that activated peroxydisulfate in the presence of formate as an additive is a convenient method for the mineralization of substrates that are refractory to oxidation, such as perchlorinated hydrocarbons and TCA. This method has the advantage that leaves no toxic residues.

Kinetic study of the oxidation of phenolic derivatives of alpha,alpha,alpha-trifluorotoluene by singlet molecular oxygen [O2(1delta(g)) and hydrogen phosphate radicals.

The oxidation kinetics and mechanism of the phenolic derivatives of alpha,alpha,alpha-trifluorotoluene, 2-trifluoromethylphenol, 3-trifluoromethylphenol (3-TFMP), 4-trifluoromethylphenol and 3,5-bis(trifluoromethyl)phenol, mediated by singlet molecular oxygen, O2(1delta(g)), and hydrogen phosphate radicals were studied, employing time-resolved O2(1delta(g)) phosphorescence detection, polarographic determination of dissolved oxygen and flash photolysis. All the substrates are highly photo-oxidizable through a O2(1delta(g))-mediated mechanism. The phenols show overall quenching constants for O2(1delta(g)) of the order of 10(6) M(-1) s(-1) in D2O, while the values for the phenoxide ions in water range from 1.2 x 10(8) to 3.6 x 10(8) M(-1) s(-1). The effects of the pH and polarity of the medium on the kinetics of the photo-oxidative process suggest a charge-transfer mechanism. 2-Trifluoromethyl-1,4-benzoquinone is suspected to be the main photo-oxidation product for the substrate 3-TFMP. The absolute rate constants for the reactions of HPO4*- with the substrates range from 4 x 10(8) to 1 x 10(9) M(-1) s(-1). The 3-trifluoromethylphenoxyl radical was observed as the organic intermediate formed after reaction of 3-TFMP with HPO4*-, yielding 2,2'-bis(fluorohydroxymethyl)biphenyl-4,4'-diol as the end product. The observed results indicate that singlet molecular oxygen and hydrogen phosphate radicals not only react at different rates with the phenols of alpha,alpha,alpha-trifluorotoluene, but the reactions also proceed through different reaction channels.