Improvement of ferrioxalate assisted Fenton and photo-Fenton processes for paracetamol degradation by hydrogen peroxide dosage.

This work aimed to investigate the impact of hydrogen peroxide (HP) punctual dosage on paracetamol (PCT) degradation, through Fenton and photo-Fenton processes under near-neutral pH conditions, using ferrioxalate and artificial sunlight. The assays were performed using a D-optimal experimental design, to statistically evaluate the influence of radiation (ON or OFF), HP concentration (94.5-756 mg L-1), and HP dosage (YES or NO), on PCT conversion. The optimal conditions determined from the study were: HP = 378 mg L-1, DOS = YES, and RAD = ON, achieving a predicted PCT conversion of 99.68% in 180 min. This result obtained from the model was very close to the experimental one (98.80%). It was verified that HP dosage positively influenced the iron catalytic cycle since higher Fe2+ concentrations were reached at shorter reaction times, accelerating not only PCT conversion but also its by-products hydroquinone and 1,4-benzoquinone, leading to better performances of Fenton and photo-Fenton reactions. Under optimal conditions and employing real water matrices (an artificial matrix with inorganic anions, a real groundwater sample, and a synthetic industrial wastewater), HP dosage demonstrated the ability to mitigate the negative effects caused by the content of different ions and other organic compounds and significantly improve HP consumption in challenging wastewater conditions.

Reaction kinetics formulation with explicit radiation absorption effects of the photo-Fenton degradation of paracetamol under natural pH conditions.

The degradation of paracetamol (PCT) in an aqueous medium using the Fenton and photo-Fenton reactions was investigated. The aim of this research was the development of a kinetic model based on a reaction mechanism, which includes two main intermediates of PCT degradation and the local volumetric rate of photon absorption (LVRPA). Ferrioxalate was used as a catalyst and the working pH was adjusted to 5.5 (natural pH). Experimental work was planned through a D-optimal experimental design and performed in a flat plate reactor irradiated by a solar simulator. Hydrogen peroxide (HP) concentration, reaction temperature, and radiation level were the operating parameters. The photo-Fenton reaction allowed to reach a minimum relative PCT concentration of 2.01% compared to 5.04% achieved with Fenton reaction. Moreover, the photo-Fenton system required a 50% shorter reaction time and lower HP concentration than in dark conditions (90 min and 189 mg L-1 vs. 180 min and 334 mg L-1, respectively). The experimental results were used to estimate the kinetic parameters of the proposed kinetic model employing a nonlinear, multi-parameter regression method. The values obtained from the normalized root-mean-square error (14.52, 1.96, 4.36, 13.16, and 8.72 % for PCT, benzoquinone, hydroquinone, HP, and oxalate, respectively) showed a good agreement between the predicted and experimental data.

Photo-Fenton degradation of a herbicide (2,4-D) in groundwater for conditions of natural pH and presence of inorganic anions.

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.