Application of catalytic ozonation using Y zeolite in the elimination of pharmaceuticals in effluents from municipal wastewater treatment plants.

Catalytic ozonation using faujasite-type Y zeolite with two different SiO2/Al2O3 molar ratios (60 and 12) was evaluated for the first time in the removal of 25 pharmaceutical compounds (PhCs) present in real effluents from two municipal wastewater treatment plants both located in the Mediterranean coast of Spain. Additionally, control experiments including adsorption and direct ozonation, were conducted to better understand the fundamental aspects of the different individual systems in wastewater samples. Commercial zeolites were used in sodium form (NaY). The results showed that the simultaneous use of ozone and NaY zeolites significantly improved the micropollutants degradation rate, able to degrade 95 % of the total mixture of PhCs within the early 9 min using the zeolite NaY-12 (24.4 mg O3 L-1 consumed), while 12 min of reaction with the zeolite NaY-60 (31 mg O3 L-1 consumed). In the case of individual experiments, ozonation removed 95 % of the total mixture of PhCs after 25 min (46.2 mg O3 L-1 consumed), while the direct adsorption, after 60 min of contact time, eliminated 30 % and 44 % using the NaY-12 and NaY-60 zeolites, respectively. Results showed that the Brønsted acid sites seemed to play an important role in the effectiveness of the treatment with ozone. Finally, the environmental assessment showed that the total risk quotients of pharmaceuticals were reduced between 87 %-99 % after ozonation in the presence of NaY-60 and NaY-12 zeolites. The results of this study demonstrate that catalytic ozonation using NaY zeolites as catalysts is a promising alternative for micropollutant elimination in real-world wastewater matrices.

Ozonation using a stainless-steel membrane contactor: Gas-liquid mass transfer and pharmaceuticals removal from secondary-treated municipal wastewater.

A tubular porous stainless steel membrane contactor was characterized in terms of ozone-water mass transport, as well as its application in removing 23 pharmaceuticals (PhACs) detected in the secondary-treated municipal wastewater, under continuous mode operation. The volumetric mass transfer coefficient (KLa) was evaluated based on liquid flow rate, gas flow rate, and ozone gas concentration. The KLa values were substantially improved with an increment in liquid flow rate (1.6 times from 30 to 70 dm3 h-1) and gas flow rate (3.6 times from 0.30 to 0.85 Ndm3 min-1) due to the improved mixing in the gas-liquid interface. For the lowest liquid flow rate (30 dm3 h-1), the water phase boundary layer (82%) exhibited the major ozone transfer resistance, but it became almost comparable with membrane resistance for the highest liquid flow rate (70 dm3 h-1). Additionally, the influence of the specific ozone dose (0.39, 0.53, and 0.69 g O3 g DOC-1) and ozone inlet gas concentration ( [Formula: see text]  = 27, 80, and 134 g Nm-3) were investigated in the elimination of 23 PhACs found in secondary-treated municipal wastewater. An ozone dose of 0.69 g O3 g DOC-1 and residence time of 60 s resulted in the removal of 12 out of the 23 compounds over 80%, while 17 compounds were abated above 60%. The elimination of PhACs was strongly correlated with kinetic reaction constants values with ozone and hydroxyl radicals (kO3 and kHO•), leading to a characteristic elimination pattern for each group of contaminants. This study demonstrates the high potential of membrane contactors as an appealing alternative for ozone-driven wastewater treatment.

Developments in the intensification of photo-Fenton and ozonation-based processes for the removal of contaminants of emerging concern in Ibero-American countries.

Contaminants of emerging concern (CECs), such as pharmaceuticals, personal care products, pesticides, synthetic and natural hormones and industrial chemicals, are frequently released into the environment because of the inability of conventional processes in municipal wastewater treatment plants to remove them. Some examples of alternative options to remove such pollutants are photo-Fenton and ozone-based processes, which are two techniques widely studied in Ibero-American countries. In fact, this region has been responsible for delivering frequently publications and conferences on advanced oxidation processes. This work is a critical review of recent developments in the intensification of the two aforementioned advanced oxidation techniques for CECs elimination in the Ibero-American region. Specifically for the photo-Fenton process (pF), this study analyses strategies such as iron-complexation with artificial substances (e.g., oxalic acid and ethylenediamine-N,N'-disuccinic acid) and natural compounds (such as humic-like substances, orange juice or polyphenols) and hybrid processes with ultrasound. Meanwhile, for ozonation, the enhancement of CECs degradation by adding hydrogen peroxide (i.e., peroxone), ultraviolet or solar light, and combining (i.e., photolytic ozonation) with catalysts (i.e., catalytic ozonation) was reviewed. Special attention was paid to how efficient these techniques are for removing contaminants from water matrices, and any potentialities and weak points of the intensified processes.