Enhancing the visible-light photoactivity of silica-supported TiO2 for the photocatalytic treatment of pharmaceuticals in water.

Catalyst samples based on SiO2-supported TiO2 were prepared with the incorporation of Ag (metal), S (nonmetal), and ZnO@S (semiconductor and nonmetal). The materials were evaluated regarding their morphological, optical, and crystalline properties as well as their photoactivity under visible and ultraviolet light toward the degradation rate of a model emerging pollutant, acetaminophen (ACT). All modified materials exhibited improved performance over the undoped catalyst. The Ag-doped catalyst achieved the largest degradation under visible radiation (about 30% in 120 min), whereas under ultraviolet irradiation, the ZnO@S-doped sample exhibited the best performance (about 62% in 120 min). A Doehlert design was carried out to evaluate the influence of pH and temperature on the photoactivity of Ag-TiO2/SiO2. In addition, the role of each reactive species in the photodegradation reaction was investigated by radical scavenger experiments, and the superoxide radical anion O2•- was shown to be the predominant reactive species. The stability of the Ag-TiO2/SiO2 material under ultraviolet and visible light was confirmed after five successive operation cycles, showing a reasonable (about 50%) loss of activity under visible irradiation and a slight improvement (about 13%) under UV light, as a result of the photo-reduction of Ag+. Lastly, the effect of the initial pollutant concentration showed that ACT degradation using Ag-TiO2/SiO2 follows the Langmuir-Hinshelwood kinetics, with intrinsic reaction rate k = 2.71 × 10-4 mmol L-1 min-1 under visible-light radiation.

Removal of sulfadiazine from simulated industrial wastewater by a membrane bioreactor and ozonation.

Ozonation can be used as a polishing treatment for degrading low-concentration pharmaceutical compounds recalcitrant to biological treatment, when large amounts of biodegradable organics have been previously removed by biological processes. Nevertheless, a systematic investigation has not yet been carried out for the coupled MBR + O3 process through an experimental design approach. Thereby, the purpose of this study is to evaluate the performance of different processes (membrane bioreactor-MBR, ozonation; and integrated MBR + O3) for removing the antibiotic sulfadiazine (SDZ) from a synthetic wastewater matrix of industrial interest. The MBR behavior was monitored over seven months for different parameters (pH, temperature, permeate flow, transmembrane pressure, biological oxygen demand-BOD5, chemical oxygen demand-COD, total organic carbon-TOC, solids, and SDZ concentration). Additionally, the amount of SDZ sorbed onto the sludge was characterized, an issue which is scarcely addressed in most research works. Ozonation experiments were conducted in batch mode in a 2-L glass reactor provided with openings for gas flow. For the MBR + O3 process, the effects of gas flow rate (0.1-1.5 L min-1) and inlet ozone concentration (4-12 mg L-1) on SDZ removal from the MBR permeate were systematically assessed using a Doehlert experimental design and response surface methodology. The results indicated that the MBR system showed good performance regarding organic matter removal efficiency, evaluated in terms of BOD5 (91.5%), COD (93.1%) and TOC (96.3%). In contrast, SDZ was partially removed (33%) by the MBR; in that case, the results indicated that the antibiotic was moderately removed with the sludge and partially biodegraded. In turn, the MBR + O3 system showed excellent performance for removing SDZ (100%), TOC (97%), BOD5 (94%) and COD (97%). The statistical analysis confirmed that the influence of ozone gas flow rate upon the SDZ removal rate was more important than that exhibited by inlet ozone concentration. Therefore, coupling MBR and ozone can be considered a promising alternative for point source treatment of antibiotic production wastewater.