Photocatalytic decomposition of selected estrogens and their estrogenic activity by UV-LED irradiated TiO2 immobilized on porous titanium sheets via thermal-chemical oxidation.

The removal of endocrine disrupting compounds (EDCs) remains a big challenge in water treatment. Risks associated with these compounds are not clearly defined and it is important that the water industry has additional options to increase the resiliency of water treatment systems. Titanium dioxide (TiO2) has potential applications for the removal of EDCs from water. TiO2 has been immobilized on supports using a variety of synthesis methods to increase its feasibility for water treatment. In this study, we immobilized TiO2 through the thermal-chemical oxidation of porous titania sheets. The efficiency of the material to degrade target EDCs under UV-LED irradiation was examined under a wide range of pH conditions. A yeast-estrogen screen assay was used to complement chemical analysis in assessing removal efficiency. All compounds but 17ß-estradiol were degraded and followed a pseudo first-order kinetics at all pH conditions tested, with pH 4 and pH 11 showing the most and the least efficient treatments respectively. In addition, the total estrogenic activity was substantially reduced even with the inefficient degradation of 17ß-estradiol. Additional studies will be required to optimize different treatment conditions, UV-LED configurations, and membrane fouling mitigation measures to make this technology a more viable option for water treatment.

Photocatalytic decomposition of organic micropollutants using immobilized TiO2 having different isoelectric points.

Organic micropollutants found in the environment are a diverse group of compounds that includes pharmaceuticals, personal care products, and endocrine disruptors. Their presence in the aquatic environment continues to be a concern as the risk they pose towards both the environment and human health is still inconclusive. Removal of these compounds from water and wastewater is difficult to achieve and often incomplete, but UV-TiO2 is a promising treatment approach. In this study, the efficiency of titanium dioxide (TiO2) immobilized on porous supports were tested for treatment of target pharmaceuticals and their metabolites under UV-LED exposure, a potential low energy and cost effective alternative to conventional UV lamps. Immobilization was completed using two different methods: (1) dip coating of TiO2 onto quartz fiber filters (QFT) or (2) thermal-chemical oxidation of porous titanium sheets (PTT). Comparison against experimental controls (dark QFT, dark PTT, and photolysis using UV-LED only) showed that UV-LED/PTT and UV-LED/QFT treatments have the potential to reduce the concentrations of the target compounds. However, the treatments were found to be selective, such that individual pharmaceuticals were removed well using QFT and PTT but not both. The complementary treatment behavior is likely driven by electrostatic interactions of charged compounds with the membranes. QFT membranes are negatively charged at the experimental pH (4.5-5) while PTT membranes are positively charged. As a result, cationic compounds interact more with QFT while anionic compounds with PTT. Neutral compounds, however, were found to be recalcitrant under any treatment conditions suggesting that ionic interactions were important for reactions to occur. This behavior can be advantageous if specificity is required. The behavior of pharmaceutical metabolites is similar to the parent compounds. However, isomeric metabolites of atorvastatin with functional groups in para and ortho configurations behave differently, suggesting that the positioning of functional groups can have an impact in their interaction with the immobilized TiO2. It was also apparent that PTT can be reused after cleaning by heat treatment. Overall, these newly synthesized membrane materials have potential applications for treatment of trace organic contaminants in water.