Many authors undertook the chemical characterisation of the leachates generated by the municipal landfills. The review of the data of the literature (see [1]) shows that several separative and analytical techniques were primarily used i.e. the ultrafiltration, the liquid-liquid extraction, the permeation chromatography on Sephadex gels, the adsorption on Amberlite XAD resins, and the gas chromatography. This led us to use a different method: the high performance size exclusion chromatography (HPSEC).We carried out a preliminarily study [1], which showed that leachates from domestic wastes contain molecules which could be filed in two main groups according to their molecular weights: one constituted of molecules of AMW (Apparent Molecular Weight) lower than 1000 Da and the other one with molecules of AMW higher than 10000 Da. Few products of intermediate molecular weights are present. Simultaneous monitoring of the samples by UV absorbance, fluorescence and evaporative light scattering (ELSD) reveals the diversity of the physico-chemical characteristics of the separated compounds. A thorough spectrometric study [2] enabled us to validate the choice of excitation/emission couples characteristic of the substances so-called humic-type and protein-type compounds used in the first study. We also showed that the chromatographic elution of the molecules is biased by secondary interactions. So, in the present article we propose to study the influence of these interactions on chromatographic separation.The mechanism of steric exclusion is theoretically a purely entropic phenomenon, which warrants for the observed relation between the volume of elution and the hydrodynamic volume of the eluted molecule. One however notes experimental variations in retention times either due to adsorption (elution delayed) or exclusion (elution advanced). This is to say that interactions between the eluted molecules and the stationary phase modify the elution order of compounds with definite molecular weights. In aqueous solvents, very polar ionised groups are exposed at the water-soluble compounds surface and secondary enthalpic interactions are observed [3][4][5]. They are due to ion-exchange and ionexclusion effects, hydrophobic interactions and hydrogen bonds. The solute-support interactions are of course undesirable for the study of the molecular weight distribution of the molecules but they can be made profitable for the optimisation of their separation. These interactions were previously described [4,6,7] and it was shown that the choice of the eluent is particularly critical in aqueous size exclusion chromatography. It is not trivial to eliminate such interactions but they can be, at least, strongly reduced by judiciously choosing the eluent properties (pH, ionic strength, addition of organic co-solvent...) [7]. Sodium nitrate is often preferred for the elution of humic substances in HPSEC. At a 20 mM concentration in the eluent, the elution of the fulvic acids on both polymeric-and silica-based columns is weakly disturbed by the io...