Evaluation of natural organic matter changes from Lake Hohloh by three-dimensional excitation–emission matrix fluorescence spectroscopy during TiO2/UV process

• The TiO2/UV degradation of NOM was monitored with EEMs fluorescence spectroscopy.
• NOM adsorption on TiO2 at acid pH led to a high decrease of fluorescence intensity.
• NOM adsorption at pH = 10 led to a negligible changes on EEMs spectral shapes.
• EEMs show TiO2/UV degradation of NOM was due to the break-up of the larger molecules.
• The reduction of fluorescence intensity of NOM led to a decrease of THMs and AOXs.

This study shows the changes of natural organic matter (NOM) from Lake Hohloh, (Black Forest, Germany) during heterogeneous photocatalysis with TiO2 (TiO2/UV). The effect of pH on the adsorption of NOM onto TiO2 in the dark and TiO2/UV degradation of NOM was followed using three-dimensional excitation–emission matrix (EEM) fluorescence. At pH values between 4 and 9, the NOM was adsorbed onto TiO2 in the dark with a greater decrease in the fluorescence intensity and in the spectral shapes, especially under acidic pH conditions. However, at pH = 10 there was not adsorption on NOM which led to a negligible changes the fluorescence intensity. A significant high linear correlation was observed between the DOC adsorption onto TiO2 and the maximum fluorescence intensity. Additionally, the NOM adsorption onto TiO2 and its TiO2/UV degradation shifted the fluorescence maxima toward shorter wavelengths in the EEM contour plots, with a decrease in aromaticity. These changes were accompanied by a substantial decrease in the organically bound halogens adsorbable on activated carbon (AOXFP) and the trihalomethane formation potential (THMFP). Thus, the decrease in maximum fluorescence intensity can be used as an indicator of AOXFP and TTHMFP removal efficiency. Therefore, fluorescence spectroscopy is a robust analytical technique for evaluate TiO2/UV removal of NOM.

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