The influence of various factors on the removal efficiency of selected pharmaceuticals by membrane filtration was investigated. Several commercial polymer membranes were used for nanofiltration (NF) from various manufacturers. The studies were conducted for ibuprofen (IBF), amoxicillin (AMX), diclofenac (DCF), tetracycline (TRC), salicylic acid (SA) and acetylsalicylic acid (ASA). The influence of the structure and properties of the tested compounds on the retention coefficient and filtration rate was investigated. The influence of pH on the filtration parameters was also checked. The properties of selected membranes influencing the retention of pharmaceuticals and filtrate flux were analysed. An extensive analysis of the retention coefficients dependence on the contact angle and surface free energy was performed. It was found that there is a correlation between the hydrophilicity of the membrane and the effectiveness and efficiency of the membrane. As the contact angle of membrane increased, the flow rate of the filtrate stream increased, while the retention coefficient decreased. The studies showed that the best separation efficiency was achieved for compounds with a molecular weight (MW) greater than 300 g/mol. During the filtration of pharmaceuticals with MW ranging from 300 to 450 g/mol, the type of membrane used practically did not affect the filtration efficiency and a high degree of retention was achieved. In the case of low MW molecules (SA and ASA), a significant decrease in the separation efficiency during the process was noted.

The possibility of removing tetracycline (TRC) from water in an integrated advanced oxidation and membrane filtration process was investigated. Ozonation and UV/H₂O₂ photooxidation were applied for the destruction of TRC. Six oxidation products (OPs) retaining the structural core of TRC have been identified. One new TRC oxidation product, not reported so far in the literature, was identified—ethyl 4-ethoxybenzoate. All identified OPs were effectively retained on the membrane in the nanofiltration process. However, chemical oxygen demand (COD) measurements of the filtrates showed that in the case of UV/H₂O₂ oxidation, the OPs passed through the membrane into the filtrate. Various water matrices were used in the research, including the river water untreated and after ozone treatment. It has been shown that organic matter present in surface water can improve pharmaceutical retention, although it contributes to significant membrane fouling. Pre-ozonation of the river water reduced the membrane fouling. The XPS analysis was used to show ozone and H₂O₂ influence on the top polymer layer of the membrane. It was shown that the oxidants can damage the amide bond of the polyamide.

The aim of this study was to investigate the effect of hydrogen peroxide on the UVC photolysis of diclofenac (DCF) in aqueous solution. The experimental results confirmed very high effectivity of UVC direct photolysis of diclofenac. Moreover, it was found that H₂O₂/UV only slightly improved photodegradation; however, the addition of hydrogen peroxide into the reaction system affected the mechanism of DCF decomposition. Kinetics of the DCF reaction with ^⋅OH radicals in the UV/H₂O₂ process was determined. For both processes, namely, photolysis and UV/H₂O₂, an in-depth analysis focused on the formation of phototransformation products of DCF (TPs) was performed. To the best of our knowledge, such comprehensive comparison of diclofenac photodegradation via UVC photolysis and UV/H₂O₂ has not been presented so far. Although there were no significant differences with regard to the rate of diclofenac degradation by photolysis and UV/H₂O₂, different oxidation products were found to be associated with the two considered processes. Furthermore, the H₂O₂/UV treatment increased toxicity towards Vibrio fischeri, while direct UVC photolysis had no significant effect on toxicity. The increase in toxicity can be attributed to the breakdown of DCF and formation of much more toxic TPs in the course of the H₂O₂/UVC process.

Abstract