Advanced oxidation and a metrological strategy based on CLC-MS for the removal of pharmaceuticals from pore & surface water.

In this work, it is studied the photolysis, electrolysis, and photo-electrolysis of a mixture of pharmaceutics (sulfadiazine, naproxen, diclofenac, ketoprofen and ibuprofen) contained in two very different types of real water matrices (obtained from surface and porewater reservoirs), trying to clarify the role of the matrix on the degradation of the pollutants. To do this, a new metrological approach was also developed for screening of pharmaceuticals in waters by capillary liquid chromatography mass spectrometry (CLC-MS). This allows the detection at concentrations lower than 10 ng mL-1. Results obtained in the degradation tests demonstrate that inorganic composition of the water matrix directly influences on the efficiency of the drugs removal by the different EAOPs and better degradation results were obtained for experiments carried out with surface water. The most recalcitrant drug studied was ibuprofen for all processes evaluated, while diclofenac and ketoprofen were found to be the easiest drugs for being degraded. Photo-electrolysis was found to be more efficient than photolysis and electrolysis, and the increase in the current density was found to attain a slight improvement in the removal although with an associated huge increase in the energy consumption. The main reaction pathways for each drug and technology were also proposed.

UV-irradiation and BDD-based photoelectrolysis for the treatment of halosulfuron-methyl herbicide.

This paper reports the development of a novel photoelectrochemical (PEC) oxidation technique based on UV-C irradiation and boron-doped diamond (BDD) anode and its application for the effective removal of the commercial herbicide halosulfuron-methyl (HSM). The study evaluated the influence of the following key operating variables in the photoelectrochemical process: current density, pH, temperature, and initial HSM concentration. With regard to HSM degradation/mineralization, the application of high current densities was found to be more advantageous once it promoted a more rapid degradation and mineralization, with 96% of total organic carbon removal, though the process became more energy-demanding over time. The initial concentration of HSM did not modify the relative degradation rate, though the degradation process became more efficient as expected in a mass-transfer controlled process. The use of acidic pH (pH 3) was found to be more suitable than neutral conditions; this is probably because an anionic resonant form of HSM may be formed in neutral conditions. The temperature level was also found to affect the rate of HSM removal and the degradation efficiency. Finally, the substitution of Na2SO4 by NaCl promoted a more rapid and effective degradation; this is attributed to high production of powerful oxidants. However, only 70% mineralization was reached after 3 h of treatment; this is probably related to the formation of recalcitrant chlorinated sub-products.