Sustainable photocatalytic oxidation processes for the treatment of emerging microcontaminants

Abstract

This work investigates the elimination of new and emerging microcontaminants (EMs) from water by means of photochemical oxidation processes, namely heterogeneous and homogeneous photocatalysis. Representative compounds of artificial sweeteners (saccharin, SAC), endocrine disruptors (bisphenol-A, BPA), and pharmaceutica ls (antipyrine, AP) of high environmental persistence and widespread occurrence in the water cycle are used as case studies. Novel concepts that can make photochemica l oxidation a more cost-effective and environmentally benign technology are tested. In Chapter 4, the photocatalytic treatment of SAC and BPA is investigated. Novel submicronic anatase–rutile nanocomposite particles with tuned phase ratio are used as catalysts to increase the photocatalytic performance under UVA irradiation. At the best-assayed conditions (C0 = 3 mg/L, catalyst = 400 mg/L), SAC and BPA are completely degraded within 90 and 150 min of photocatalytic treatment, respectively. [variables: anatase-rutile ratio; initial substrate concentration; catalyst concentration; catalyst reuse; sonication during catalyst recovery] In Chapter 5, a UVA light-emitting diode (UVA-LED) and sunlight are used as irradiation sources to reduce energy requirements and environmental impacts of photocatalytic processes. The photocatalytic degradation of SAC and BPA is studied under UVA irradiation provided by either a UVA-LED or a conventional fluoresce nt blacklight UVA lamp (UVA-BL) and solar irradiation. At the best-assayed conditions (C0 = 2.5 mg/L, TiO2 = 250 mg/L), BPA is completely degraded within 20, 30, and 120 min under UVA-LED, solar, and UVA-BL irradiation, respectively. The treatment time required for the complete elimination of SAC is 20 min under UVA-LED and 90 min under UVA-BL irradiation. [variables: initial substrate concentration; catalyst concentration; water matrix; light source; reactor configuration] In Chapter 6, a comparative study is carried out among the photocatalytic systems of Chapters 4 and 5 in terms of EMs removal, photonic and energy efficiencies. Technica l and economic aspects of all the processes are assessed. LED-driven photocatalysis achieves the highest efficiency in terms of organic removal with the minimum energy consumption, rendering it the most sustainable technology for the treatment of EMs. In Chapter 7, olive mill wastewater (OMW) is used as an iron-chelating agent in the photo-Fenton reaction to obviate the need for water acidification at pH 2.8. Conventional, OMW- and EDDS-assisted photo-Fenton treatment is applied for SAC degradation in a solar compound parabolic collector (CPC). It was found that OMW forms iron complexes able to catalyse H2O2 decomposition and generate hydroxyl radicals. At the optimal OMW dilution (1:800), 90% of SAC is degraded within 75 min. [variables: pH; iron-chelating agent; initial SAC concentration; OMW dilution] In Chapter 8, other complexing and oxidising agents, namely oxalate and persulfate, are used for the intensification of AP degradation during UVA-LED photo-Fenton treatment. Neural networks are applied for process modelling and optimisation. At the optimal conditions (hydrogen peroxide = 100 mg/L, ferrous iron = 20 mg/L, oxalic acid = 100 mg/L), complete degradation of AP and 93% mineralisation is achieved within 2.5 and 60 min, respectively. [variables: initial concentration of hydrogen peroxide, ferrous iron, oxalic acid, persulfate] It is concluded that LED-driven photocatalysis is a sustainable technology for the elimination of EMs from water. Results from this work highlight the need for development and optimisation of engineering proper LED reactors. Furthermore, this work introduces a new concept towards the sustainable operation of photo-Fenton that is based on the use of wastewaters rich in polyphenols instead of pricey and hazardous chemicals for iron chelation. The addition of ferrioxalate complexes is proposed for the intensification of EMs mineralisation during UVA-LED photo-Fenton treatment. Finally, the findings of this work encourage the use of chemometric tools as predictive and optimisation tools