Elucidating physicochemical processes in the degradation of pollutants may optimize their removal from water sources. This work presents a set of elementary steps in the photocatalytic degradation of carbamazepine (CBZ), assuming a steady state approximation in an Advanced Oxidation Process (AOP) combining short-wave ultraviolet radiation (UVC), homogeneous reagent (H₂O₂) and heterogeneous (TiO₂) catalyst. Elementary steps include excitation of both reagent/catalysts by UVC photons, adsorption of CBZ on the excited TiO₂, or its oxidation by hydroxyl radicals. Assuming the steady state approximation on the intermediate products (excited TiO₂, CBZ- excited TiO₂ complex, and hydroxyl radicals), leads to rate laws for degradation of CBZ, in which UVC radiation, TiO₂, and H₂O₂ are pseudo first order at all concentrations or intensities having no direct influence on CBZ pseudo-order, whereas CBZ shifts from pseudo first order at low concentrations to pseudo-zero order at high concentrations. Several experiments to test the mechanism were conducted, by varying CBZ, H₂O₂, and TiO₂ concentrations, and UVC radiation intensities. Measured results indeed fit the suggested mechanism for the first three, but irradiation intensity appears to shift CBZ influence from pseudo-second to pseudo-first order with increased intensities. Corrected elementary steps are proposed to fit the results.

Ofloxacin is a highly efficient and widely used antibiotic drug. It is classified as a refractory pollutant due to its poor biodegradability. Consequently, it is commonly found in water sources, requiring efficient methods for its removal. Advanced Oxidation Processes (AOPs) offer efficient alternatives since those yield complete degradation not achieved in adsorption or membrane processes. Previous studies suggest ofloxacin degradation follows a pseudo-first or -second order processes, whereas for full removal of refractory pollutants – lower pseudo-orders are required. Monitoring the actual “pseudo-order” degradation kinetics of ofloxacin is needed to evaluate any proposed AOP process. This study presents a simple procedure to evaluate pseudo-orders of AOPs. Photolysis of 20 mM ofloxacin solutions follow pseudo-zero order kinetics, with half-life times (t_1/2) of approx. 60 min. TiO₂ heterogenous catalyst show to have no influence at low concentration (0.2 mg L^-1) but a significant reduction of half-life time (t_1/2 = 20 min) and increase in pseudo-order (0.8) is measured at 2.0 mg L^-1. Similar results are obtained with homogenous catalysis by 2.0 mg L^-1 H₂O₂. The combination of H₂O₂ and TiO₂ catalysts shows additional reduction in half-time life with increase in the pseudo-order to 1.2. The conclusions are (1) heterogenous and homogenous photocatalysis can effectively degrade ofloxacin, (2) combined photocatalysis yields higher pseudo-order, being less prone to achieve full removal, (3) analysis of specific pseudo-orders in AOPs of refractory pollutants helps to further elucidate the efficiency of the processes.

Carbamazepine (CBZ) is one of the most common emerging contaminants released to the aquatic environment through domestic and pharmaceutical wastewater. Due to its high persistence through conventional degradation treatments, is considered a typical indicator for anthropogenic activities. This study tested the removal of CBZ through two different clay-based purification techniques: adsorption of relatively large concentrations (20-500 μmol L-1) and photocatalysis of lower concentrations (<20 μmol L-1). The sorption mechanism was examined by FTIR measurements, exchangeable cations released, and colloidal charge of the adsorbing clay materials. Photocatalysis was performed in batch experiments under various conditions. Despite the neutral charge of carbamazepine, the highest adsorption was observed on negatively charged montmorillonite-based clays. Desorption tests indicate that adsorbed CBZ is not released by washing. The adsorption/desorption processes were confirmed by ATR-FTIR analysis of the clay-CBZ particles. A combination of synthetic montmorillonite or hectorite with low H2O2 concentrations under UVC irradiation exhibits efficient homo-heterogeneous photodegradation at μM CBZ levels. The two techniques presented in this study suggest solutions for both industrial and municipal wastewater, possibly enabling water reuse.

Poly-DADMAC (PD) is a commonly used organic polymer in water treatment, known for its effectiveness as a coagulant. However, its presence as a residue in water raises concerns related to membrane fouling and the potential formation of carcinogenic compounds. Therefore, fast and simple quantification is necessary to efficiently control and monitor the optimal dose of poly-DADMAC with minimal negative effects. This study introduces a new colorimetric quantification method for poly-DADMAC, based on complexation with a cationic dye (fast green- FG). The method was examined through varying conditions which included different analytical and commercial poly-DADMAC formulations and concentrations. The experiments confirm its effectiveness in quantifying poly-DADMAC with a detection limit of 3.22 µg L^-1 (0.02 µM based on monomers' molecular weight), which is one order of magnitude lower than regulatory requirements (50 µg L^-1). To validate the method, the effect of pH was examined, and implementation demonstrations were conducted on cyanobacteria and cowshed polluted water samples. This research introduces a fast, cost-effective innovative method to accurately quantify poly-DADMAC, enhancing water treatment strategies for high-quality purification and water reuse