Alam G. Trovó

Degradation of caffeine by photo-Fenton process: optimization of treatment conditions using experimental design.

The degradation of caffeine in different kind of effluents, via photo-Fenton process, was investigated in lab-scale and in a solar pilot plant. The treatment conditions (caffeine, Fe(2+) and H(2)O(2) concentrations) were defined by experimental design. The optimized conditions for each variable, obtained using the response factor (% mineralization), were: 52.0 mg L(-1)caffeine, 10.0 mg L(-1)Fe(2+) and 42.0 mg L(-1)H(2)O(2) (replaced in kinetic experiments). Under these conditions, in ultrapure water (UW), the caffeine concentration reached the quantitation limit (0.76 mg L(-1)) after 20 min, and 78% of mineralization was obtained respectively after 120 min of reaction. Using the same conditions, the matrix influence (surface water - SW and sewage treatment plant effluent - STP) on caffeine degradation was also evaluated. The total removal of caffeine in SW was reached at the same time in UW (after 20 min), while 40 min were necessary in STP. Although lower mineralization rates were verified for high organic load, under the same operational conditions, less H(2)O(2) was necessary to mineralize the dissolved organic carbon as the initial organic load increases. A high efficiency of the photo-Fenton process was also observed in caffeine degradation by solar photocatalysis using a CPC reactor, as well as intermediates of low toxicity, demonstrating that photo-Fenton process can be a viable alternative for caffeine removal in wastewater.

Coupling coagulation, flocculation and decantation with photo-Fenton process for treatment of industrial wastewater containing fipronil: Biodegradability and toxicity assessment

This work reports the treatment of wastewater containing the insecticide fipronil, integrating coagulation, flocculation and decantation in the photo-Fenton process. Under the best concentration of the coagulant - Fe(3+) (56 mg L(-1)), the suspended solids and total fipronil concentrations decreased respectively from 7000 and 20.9 mg L(-1) to 590 and 2.2 mg L(-1), but without reduction in dissolved organic carbon - DOC (1760 mg C L(-1)) and acute toxicity to Artemia salina (100%). Subsequently, the photo-Fenton process was applied as alternative of pre- or complete treatment, taking into account toxicity and biodegradability (given by biochemical oxygen demand after five days - BOD5/chemical oxygen demand - COD ratio) assessment. The best DOC and COD removal were reached with 60 and 6723 mg L(-1) of Fe(2+) and H2O2, respectively. Under these conditions, after 60 min of irradiation, 57% of DOC and 74% of COD were removed, with a decrease in acute toxicity to A. salina from 100% to 13% and an increase in the BOD5/COD ratio from 0.052 to 1.0. With these parameters, the integration of coagulation/flocculation/decantation and photo-Fenton processes may be an alternative to the pre- or complete treatment of wastewater containing fipronil.

Degradation of the commercial herbicide glyphosate by photo-fenton process: evaluation of kinetic parameters and toxicity

Parameters that influence the efficiency of the degradation of glyphosate (addition of Fe2+, simultaneous addition of Fe2+ and Fe3+ at a 1:1 (Fe2+/Fe3+) molar ratio, addition of oxalate and of H2O2) were evaluated at lab-scale. Synergic effects on its degradation and release of phosphate were observed using Fe2+/Fe3+, as well as adding oxalate. On the other hand, the concentration increase of Fe2+/Fe3+, oxalate and H2O2 did not promote a linear increase of glyphosate mineralization and release of phosphate. Using high concentrations of these species, the efficiency of glyphosate mineralization and release of phosphate was constant or even decreased. Under optimized conditions (0.27 mmol L-1 of Fe2+/Fe3+; 1.13 mmol L-1 of oxalate and 10.3 mmol L-1 of H2O2), close results for mineralization and release of phosphate were obtained in lab-scale and using a solar pilot plant. A direct ratio between reducing the toxicity and glyphosate concentration was also observed.

Photolytic degradation of chloramphenicol in different aqueous matrices using artificial and solar radiation: reaction kinetics and initial transformation products

The photodegradation of cloramphenicol (CAP) in ultrapure water (UW), untreated surface water (USW), and treated effluent from sewage treatment plant (TESTP) in laboratory scale and pilot scale, was evaluated using solar and artificial radiation. The results show, in all cases, that the CAP degradation occurs according to pseudo-first order kinetics, with the apparent degradation rate constants (kapp) following the order UW ≡ USW > TESTP. The kapp and half-life were strongly influenced by the radiation source. Mono- and di-hydroxyl transformation products were identified in UW after 40 min of solar irradiation, while the acute toxicity to Artemia salina increased from 35% to 100%, respectively after 180 and 1440 min of artificial and solar irradiation (94 and 132 kJ L-1), when 99.2 and 97.7% of CAP degradation occurred. The transformation products did not present antimicrobial activity.

Applications of Mesoporous Ordered Semiconductor Materials — Case Study of TiO2

TiO2 is a promising material for technological applications for its versatility [1-4], abundance, low toxicity, good chemical stability, photosensitivity and photostability [5-8]. In nature, it is found mainly in the mineral ilmenite [9], that can be processed industrially by two different routes [10]: The first, involves the reaction of the concentrate of ilmenite with hot sulphuric acid, resulting in the formation of sulphates of titanium, Fe(II) and Fe(III), being these last eliminat‐ ed by centrifugation, after cooling. The final solution is then purified and hydrolyzed to produce pure TiO2 [11]. The other usual way of obtaining consists in combining the ore with coke and gaseous chlorine under heating, resulting in CO2 and a spongy material rich in TiCl4. The reaction product is subjected to successive fractional distillation, with the formation of TiCl2 and TiCl3, due to stability of titanium in other degrees of oxidation. The different precursors of titanium are hydrolyzed, forming titanium dioxide [12].

Treatment of Effluent from a Factory of Paints Using Solar Photo-Fenton Process

We evaluated the use of Fenton reactions induced by solar radiation in the treatment of effluent from a factory of paints for buildings, after prior removal of the suspended solids. The increase of H2O2 concentration from 100 to 2500 mg L−1 for a [Fe2

Efficient Mineralization of Paracetamol Using the Nanocomposite TiO2/Zn(II) Phthalocyanine as Photocatalyst

The photocatalytic performance of a composite based on the association of TiO2 and 2.5 wt.% of zinc(II) phthalocyanine (TiO2/ZnPc) was evaluated towards the mineralization of paracetamol and compared to that observed for the bare oxide in different pH and H2O2 concentrations. The results show that the photocatalytic performances were influenced by the pH, with maximum efficiency around the isoelectric point. Mineralization efficiencies between 86-91% was obtained using TiO2/ZnPc in pH 5.5-6.8, with 33 mg L-1 of H2O2, ca. 15% higher than that observed with TiO2. The mineralization efficiencies using bare TiO2 and TiO2/ZnPc were respectively 112 and 18% lower in the absence of H2O2. The better performance of TiO2/ZnPc is related to its extended light absorption and non-uniform coating of the TiO2 surface by ZnPc aggregates. Above pH 6.8, the mineralization efficiencies decrease for both photocatalysts, although the consumption of H2O2 remains above 90%, due to its decomposition in alkaline pH.

Biodiesel Wastewater Treatment by Coagulation-Flocculation: Evaluation and Optimization of Operational Parameters

In this study the coagulation-flocculation process was evaluated as an alternative for treatment of biodiesel wastewater. The role of two coagulants, Al3+ and Fe3+, as well as its dosage, pH, treatment time, stirring and aeration were evaluated. It was observed that in the treatment using Al3+ the pH of the effluent (9.7) does not need to be adjusted, while for Fe3+ a previous adjustment to pH 5.0 was necessary. On the other hand, a high concentration of Al3+ (243 mg L-1) and a relatively long treatment time (70 min) were required to reach more than 96% of turbidity removal, when compared to the processing using Fe3+ (56 mg L-1 and 53 min), attributed to the formation of different mole fractions of hydrolyzed cationic species. Under the optimized conditions, more than 96% of turbidity, apparent color and suspended solids, and 82% of oil and fats were removed.

Treatment of Sanitary Landfill Leachate by Photo-Fenton Process: Effect of the Matrix Composition

In this study it was evaluated the role of the composition of sanitary landfill leachate on the removal of dissolved organic carbon (DOC) by photo-Fenton process. The composition of the matrix (high turbidity and color, as well as presence of inorganic ions sulfate and chloride) does not reduce the efficiency of DOC removal by photo-Fenton reactions, but influences significantly the reaction time and consumption of H2O2. An expressive increase in the efficiency of DOC removal occurred for concentrations of Fe2+ between 50 and 100 mg L-1, remaining constant in the range between 100 and 200 mg L-1. On the other hand, the pre-treatment of this effluent by coagulation-flocculation before the photo-Fenton process is recommended, since a similar efficiency of DOC removal, between 70 and 77%, was achieved using only 17% of the time and 7% of H2O2 necessary for the treatment of raw leachate treatment.

Degradation of the herbicide paraquat by photo-fenton process: optimization by experimental design and toxicity assessment

This study describes the influence and optimization of Fentons reagent (concentration of Fe2+ and H2O2 ) on the efficiency of mineralization of the herbicide paraquat (PQT, 50 mg L-1) in water, after 60 min (equivalent to 642 kJ L-1 of accumulated UVA radiation) treatment by photo-Fenton process in laboratory scale, using central composite design (CCD). Under optimized conditions, kinetic experiments were done, evaluating the PQT removal, its mineralization and toxicity in laboratory scale, using artificial irradiation, and in a pilot plant under solar irradiation. The same removal efficiency and mineralization of PQT were obtained in both reactors. The toxicity of the samples, estimated in terms of mortality of Artemia salina, decreases simultaneously with the decay of concentration of PQT, suggesting the formation of intermediates of lower toxicity. In this way, the solar photo-Fenton process can be considered as a viable alternative for the treatment of wastewater containing PQT.