BACKGROUND: The study evaluated the relationship between particle size distribution (PSD) of chemical oxygen demand(COD) and treatability of leachate generated by organic waste. PSD determinations were performed together with physico-chemical and biological treatability studies. Leachate biodegradation was also evaluated by means of oxygen uptake rate (OUR) profiles and experimental results were used for calibration of the adopted mathematical model. RESULTS: The leachate was characterized by a COD content of 80 000 mg L(-1) in summer. PSD analysis showed a bimodal distribution with around 60% of the COD below 2 nm and 25% above 1600 nm. Chemical treatment by lime and alum provided limited COD removal (30-35%). The extent of COD removal was higher than the particulate COD fraction above 1600 nm, it also occurred in the soluble range below 2 nmthrough adsorption. A modeling study indicated three major COD fractions that could be correlated with PSD analysis: readily biodegradable COD and slowly biodegradable COD in the soluble range and hydrolyzable COD fraction in the particulate range. CONCLUSION: PSD-based COD fractionation adequately explained limitations of chemical treatment efficiency; it was also a reliable complement to the currently used respirometric tests for biodegradation, providing insight to the fate of different COD fractions included in the soluble range (<2 nm) and yielding concrete supporting information on the generation of soluble residual microbial products. (C) 2011 Society of Chemical Industry