RESUMO

In this work, the use of natural organic wastes (orange and lemon peels) as sources of citric acid was evaluated along with the application of the photoelectro-Fenton (PEF) system under non-modified pH as a novel alternative to degrade a complex mixture of pharmaceuticals: sulfamethoxazole (SMX-7.90 × 10-5 mol/L) and trimethoprim (TMP-6.89 × 10-5 mol/L). The system was equipped with a carbon felt air diffusion cathode (GDE) and a Ti/IrO2 anode doped with SnO2 (DSA). A 3.6 × 10-5 mol/L solution of commercial citric acid was used as a reference. The pharmaceuticals' evolution in the mixture was followed by high-performance liquid chromatography (HPLC). The addition of natural products showed an efficient simultaneous degradation of the antibiotics (100% of SMX and TMP at 45 min and 90 min, respectively) similar to the performance produced by adding the commercial citric acid to the PEF system. Moreover, the addition of natural products allowed for an increment of biodegradability (100% removal of TOC by a modified Zahn Wellens test) and a decrease in ecotoxicity (0% in the bioassay with D. Magna) of the treated solutions. The antibacterial activity was eliminated after only 45 min of treatment, suggesting that the degradation by-products do not represent a significant risk to human health or the environment in general. Results suggest that, because of the efficient formation of Fe-citrate complexes, the PEF could be enhanced by the addition of natural organic wastes as a sustainable alternative ecological system for water contaminated pharmaceuticals. Additionally, the potential of reusing natural organic wastes has been exposed, contributing to an improved low-cost PEF by decreasing the environmental contamination produced by this type of waste.

Assuntos

RESUMO

The effects of four inorganic anions (Cl-, SO42-, HCO3-, NO3-) usually present in groundwater were investigated on the photo-Fenton degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). A kinetic model derived from a reaction sequence is proposed using the ferrioxalate complex as iron source at pH close to natural conditions (pH = 5). It was demonstrated that oxalate not only maintained iron in solution for the natural groundwater system, but also increased the photochemical activation of the process. Results showed that the minimum conversion of 2,4-D for the simulated groundwater after 180 min was 63.80%. This value was only 14.1% lower than the conversion achieved without anions. However, with all anions together, the consumption of hydrogen peroxide (HP) per mole of herbicide showed an increase with respect to the test without anions. Only one kinetic parameter was estimated for each anion applying a nonlinear regression method. Subsequently, these optimized kinetic constants were used to simulate the system behaviour, considering the influence of all the studied anions together. A good agreement between kinetic model predictions and experimental data was observed, with the following errors: RMSE2,4-D = 3.98 × 10-3 mM, RMSEHP = 1.83 × 10-1 mM, RMSEOX = 1.39 × 10-2 mM, and RMSE2,4-DCP = 5.59 × 10-3  mM.

RESUMO

This study evaluated, at laboratory scale, if the using iron naturally present (0.3 mg L-1) and adding 10 mg L-1 of hydrogen peroxide was effective to remove 24.3 mgL-1 of 2,4-dichlorophenoxyacetic acid (2,4-D) from groundwater samples by simulated solar irradiation (global intensity = 300 W m-2). Under these conditions, the degradation of 2,4-D reached 75.2 % and the apparition of its main oxidation byproduct 2,4-dichlorophenol (DCP) was observed. On the other hand, pH exhibited an increasing from 7.0 to 8.3 during the experiment. Experiments using Milli-Q water at pH 7.0, iron, and H2O2 concentrations of 0.3 and 10 mg L-1, respectively, were carried out in order to study the effect of ions such as carbonate species, phosphate, and fluoride in typical concentrations often found in groundwater. Ion concentrations were combined by using a factorial experimental design 23. Results showed that carbonates and fluoride did not produce a detrimental effect on the 2,4-D degradation, while phosphate inhibited the process. In this case, the pH increased also from 7.0 to 7.95 and 8.99. Effect of parameters such as pH, iron concentration, and hydrogen peroxide concentration on the 2,4-D degradation by the photo-Fenton process in groundwater was evaluated by using a factorial experimental design 23. Results showed that the pH was the main parameter affecting the process. This study shows for the first time that using the photo-Fenton process at circumneutral pH and iron naturally present seems to be a promising process to remove pesticides from groundwater.

Assuntos