The combination of asymmetrical flow field-flow fractionation (AsFlFFF) with the laser-induced breakdown detection (LIBD) is presented as a powerful tool for the determination of colloid size distribution at trace particle concentrations. Detection limits (D1) of 1, 4, and 20 microg/L have been determined for a mixture of polystyrene reference particles with 20, 50, and 100 nm in size, respectively. This corresponds to injected masses of 1, 4, and 20 pg, which is lower than found in a previous study with the symmetrical FlFFF (SyFlFFF). The improvement is mainly due to the lower colloid background discharged from the AsFlFFF channel. The combined method of AsFlFFF-LIBD is then applied to the analysis of iron oxi/hydroxide colloids being considered as potential carriers for the radionuclide migration from a nuclear waste repository. Our LIBD arrangement is less sensitive for iron colloid detection as compared to reference polystyrene particles which results in a detection limit of approximately 240 microg/L FeOOH for the AsFlFFF-LIBD analysis. This is superior to the detection via UV-Vis absorbance and comparable to ICP-MS detection. Size information (mean size 11-18 nm) for different iron oxi/hydroxide colloids supplied by the present method is comparable to that obtained by sequential ultrafiltration and dynamic light scattering. A combined on-line ICP-MS detection is used to gain insight into the colloid-borne main and trace elements.