BACKGROUND: Fly-ash (FA) additive was evaluated for enhanced removal of organic matter during soil aquifer treatment (SAT) of a wastewater treatment plant (WWTP) effluent in five 0.50 m length columns (diameter 0.1 m) in parallel. RESULTS: The characteristic behavior of dissolved organic matter (DOM) was examined for the stratum matrix configurations of both natural soil and a mixture of soil and FA. Incubation and fractionation experiments indicated that FA additive within the SAT columns would enhance the bulk adsorption of hydrophobic fractions, but decrease the biodegradation of the hydrophilic fraction simultaneously. The configuration design of an upper 0.25 m soil layer and a mixture of FA and soil underneath could make use of the functions of both FA adsorption and biodegradation within soil, which could lead to a further fractional removal of dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP). Moreover, FA additive in the SAT columns could result in a significant decrease of tryptophan-like aromatic proteins and fulvic-like components (C=C and C=O related), while the setting of the top 25 cm soil layer would lead to a further reduction of oxygen-containing functional groups. CONCLUSIONS: Based on the results, FA might serve as a supplementary material for enhancing the reduction of DOM during SAT operation. (C) 2010 Society of Chemical Industry