The surge in the use of antibiotics, especially in aquaculture, has led to development of antibiotic resistance genes, which will harm environmental and public health. One of the most commonly used antibiotics in aquaculture is oxytetracycline (OTC). Employing photocatalysis, this study compared OTC degradation efficiency of two different types of common photocatalysts, TiO2 and graphitic carbon nitride (GCN) in terms of their photochemical properties and underlying photocatalytic mechanism. For reference purpose, self-synthesized GCN from urea precursor (GCN-Urea) and commercial GCN (GCN-Commercial) were both examined. OTC adsorption-photocatalysis removal rates in pure OTC solution by TiO2, GCN-Urea and GCN-Commercial were attained at 95%, 60% and 40% respectively. Photochemical properties evaluated included light absorption, band gap, valence and conduction band positions, photoluminescence, cyclic voltammetry, BET surface area and adsorption capability of the photocatalysts. Through the evaluations, this study provides novel insights towards current state-of-the-art heterogeneous photocatalytic processes. The electron-hole recombination examined by photoluminescence is not the key factor influencing the photocatalytic efficacies as commonly discussed. On the contrary, the dominating factors governing the higher OTC degradation efficiency of TiO2 compared to GCN are the high mobility of electrons that leads to high redox capability and the high pollutant-photocatalyst affinity. These claims are proven by 86% and 40% more intense anodic and cathodic cyclic voltammetry curve peaks of TiO2 as compared to both GCNs. OTC also demonstrated 1.7 and 2.3 times higher affinity towards TiO2 than GCN-Urea and GCN-Commercial. OTC removal by TiO2 in real aquaculture wastewater only achieved 50%, due to significant inhibition effect by dissolved solids, dissolved organic matters and high ionic contents in the wastewater.
Membrane distillation (MD) is an advantageous separation process compared with pressure-driven technologies and was subsequently introduced to treat aquaculture wastewater. Harnessing a superhydrophobic membrane in an MD process is of extreme importance to prevent membrane wetting. In this work, the electrospun polypropylene (PP) membrane was surface modified by depositing an additional coating of PP via the solvent-exchange method, thereby improving the membrane's superhydrophobicity. Layer-by-layer deposition of PP caused the formation of uniform polymer spherulites on the membrane surface, which levelled up the membrane's surface roughness. A superhydrophobic surface was achieved by applying a single-layered PP coating, with static water contact angle of 152.2° and sliding angle of 12.5°. While all membranes achieved almost perfect salt rejection (up to 99.99%), the MD permeate flux improved by 30%, average of 13.0 kg/m2h, when the single-layered PP-coated membrane was used to treat the high salinity water in both 2 and 60 hr MD processes. Further layers of coating resulted in larger size of PP spherulites with higher sliding angle, followed by lowered flux in MD. The evenness of the surface coating and the size of the aggregate PP spherulites (nano-scaled) are two predominant factors contributing to the superhydrophobicity character of a membrane.
Surging growth of aquaculture industry has alarmed the public when the wastewater discharged had an adverse effect on the environment. This current study is a pioneer in the use of membrane distillation (MD) to treat real aquaculture wastewater. In addition to excellent hydrophobicity, the slippery surface of membrane used for MD is another key factor that enhances the performance of MD. The slippery surface of the membrane was tuned by layering high-viscosity and low-viscosity polypropylene (PP) polymers on the electrospun membrane by solvent-exchanged method. While the high-viscosity PP coating (PP/HV) rendered the membrane surface slippery, the low-viscosity PP coating (PP/LV) caused the fish farm wastewater to have stick-slip movement on the membrane surface. In the long-term 70-hour direct contact membrane distillation (DCMD) separation, PP/HV and PP/LV membranes can perfectly eliminate the undesirable components in the fish farm wastewater. The PP/HV membrane has registered a flux of 19.1 kg/m2·h, while the flux of PP/LV membrane was only 7.3 kg/m2·h. The PP/HV membrane also showed excellent anti-scaling properties in relative to the PP/LV membrane. This is because the PP/HV membrane promotes effortless gliding of the feed water along the surface of the membrane, while the surface of the PP/LV membrane has a static water boundary. Therefore, it can be concluded that the application of MD using the membrane coated with high-viscosity PP polymer is a feasible technology for the treatment of aquaculture wastewater.