A Comparison of Solar Photocatalytic Inactivation of Waterborne E. Coli Using Tris(2,2’-bipyridine)ruthenium(II), Rose Bengal and TiO2

Background. The development of alternative processes to eliminate pathogenic agents in water is a matter of growing interest. Current drinking water disinfection procedures, such as chlorination and ozonation, can generate disinfection by-products with carcinogenic and mutagenic potential and are not readily applicable in isolated rural communities of less-favored countries. Solar disinfection processes are of particular interest to water treatment in sunny regions of the Earth. Solar light may be used to activate a photocatalyst or photosensitizer that generates, in the presence of molecular oxygen dissolved in water, reactive oxygen species (ROS), such as the HO• radical, singlet oxygen (1O2), or superoxide (O2[bullet]), which are toxic to waterborne microorganisms. Method of Approach. Wild and collection-type Escherichia coli have been selected as model bacteria. Inactivation of such bacteria by either TiO2 nanoparticles, water-soluble tris(2,2[prime]-bipyridine)ruthenium(II) dichloride or Rose bengal (RB) subject to simulated sunlight have been compared. Although TiO2 is the prototypical material for heterogeneous photocatalysis, the other two dyes are known to generate significant amounts of 1O2 by photosensitization but have different chemical structures. The concentration of dye, illumination time, photostability, presence of scavengers, and post-treatment regrowth of bacteria have been investigated. Results. After 1 hr of solar illumination the Ru(II) complex produced a strong loss of E. coli culturability monitored with solid selective agars. Both the collection- and wild-type bacteria are sensitive to the treatment with 2–10 mg L−1 of dye. This photosensitizer showed a better inactivation effect than TiO2 and the anionic organic dye RB due to a combination of visible light absorption, photostability, and production of 1O2 and other ROS when bound to the bacterial membrane. A complete loss of culturability was observed when the initial concentration was 103 CFU mL−1, with no bacteria regrowth detected after 24 hr of the water treatment. At higher initial microorganism levels, culturability still remains and regrowth is observed. Scavengers show that the HO• radical is not involved in bacteria inactivation by photosensitization. Conclusions. A higher quantum yield of ROS generation by the sensitizing dyes compared to the semiconductor photocatalyst determines the faster sunlight-activated water disinfection of photodynamic processes. The homogeneous nature of the latter determines a more efficient interaction of the toxic intermediates with the target microorganisms. Solid supporting of the Ru(II) dye is expected to eliminate the potentials problems associated to the water-soluble dye.