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Application of photocatalysis for degradation of natural organic matter (NOM) has received wide interest during the last decades. Besides NOM, model compounds more specifically humic acids (HAs) were also studied. As a continuation of the previous research, TiO2 photocatalytic degradation of HA was investigated in the presence of clay minerals, i.e., montmorillonite (Mt) and kaolinite (Kt). Degradation of HA was expressed by the pseudo-first-order kinetic modelling of dissolved organic carbon (DOC) and UV-VIS parameters (Colour436 and UV254). A slight rate enhancement was attained for Colour436 and UV254 in the presence of either Mt or Kt. The presence of clay particles did not significantly change the DOC degradation rate of HA. The effect of ionic strength (Ca2+ loading from 5 x 10(-4) M to 5 x 1(-3) M) was also assessed for the photocatalytic degradation of sole HA and HA in the presence of either Mt or Kt. Following photocatalytic treatment, molecular size distribution profiles of HA were presented. Besides the effective removal of higher molecular size fractions (100 and 30 kDa fractions), transformation to lower molecular size fractions (<3 kDa) was more pronounced for sole HA rather than HA in the presence of clay minerals. Scanning electron microscopic images with the energy dispersive X-ray analysis confirmed the diversities in surface morphologies of the binary and ternary systems composed of HA, TiO2 and Mt or Kt both prior to and following photocatalysis. This study demonstrated that photocatalysis could be applicable for DOC degradation in the presence of clay minerals in natural waters.

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Humic acids (HA) which constitute the major subgroup of natural organic matter (NOM) are mainly composed of heterogeneous and polydisperse macromolecules. Considering the reactivities of the humic moieties towards the common coagulants during physico-chemical treatment of drinking water, different pre-oxidation conditions could exhibit various changes in humic acid structure leading to diverse reactivities towards the trivalent cations. The aim of this study was to evaluate the effects of the oxidative pre-treatment schemes applied by ozonation, TiO