The local structure of trace amounts of lead in an adsorbent matrix that contains a high concentration of iron and magnesium (Mg6Fe2(OH)16(CO3) x 3H2O) was successfully monitored by means of X-ray absorption fine structure spectroscopy combined with fluorescence spectrometry. A eutectic mixture of PbCO3 and Pb(OH)2 coagulated when Pb2+ was adsorbed from a 1.0 ppm aqueous solution, and in contrast, the major species was ion-exchanged Pb2+ in the case of adsorption from a 100 ppb aqueous solution. The difference was ascribed to the balance between the precipitation equilibrium for coagulation and the rate of the ion exchange reaction with surface hydroxyl groups.