A flow-through hyphenated analytical method has been tested that enables not only the accelerated and efficient fractionation of trace elements (TE) species in environmental solids to be achieved but allows real-time studies on the leaching process to be made. Rotating coiled columns (RCC), earlier used mainly in countercurrent chromatography, have been successfully applied to the dynamic fractionation of heavy metals in soil, sediment, and sludge samples. A ground solid sample (about 0.5 g) was retained in a PTFE rotating column as the stationary phase whereas different aqueous eluents, chosen according to recent data on the selectivity of leachants, were continuously pumped through. Elements were determined in the effluent on-line by inductively coupled plasma atomic emission spectrometry (ICP-AES). Since the flow rates used in the RCC are in good agreement with those needed for cross-flow nebulization in the ICP-AES spectrometer, both devices were coupled directly without any additional interface systems. Simultaneous investigation of the elution profiles of trace and major elements has made it possible to study the elements association in separated fractions and hence to prove the efficacy of extractants and their selectivity toward targeted mineralogical phases of samples. The close association of heavy metals with Mn oxides in the sediment and sludge samples was confirmed. The time-resolved dissolution of different organic complexes of metals was observed for the sediment sample. It was found that in sediment and sludge samples the dynamics of iron release under the action of Tamm's reagent is somewhat different from that of aluminium. In addition, the proposed method can also be applied to develop effective leaching schemes and in the analysis of environmental solids for risk assessment of their contaminants addressed to water quality and bioavailability.