This work determined the role of humic acid (HA) and fulvic acid (FA), which was extracted from the natural soil, in the interaction mechanism and microstructure of Eu(III) with pyrolusite (beta-MnO2) by using batch experiments and extended X-ray absorption fine structure (EXAFS) techniques. We combined macroscopic and spectroscopic approaches to see the evolution of the interaction mechanism and microstructure of Eu(III) with beta-MnO2 in the presence of HA or FA in comparation with that in the absence of HA or FA. The results suggested that Eu(III) interaction with beta-MnO2 was obviously affected by the addition of HA or FA. The interaction of Eu(III) with beta-MnO2 was enhanced at pH < 6.5 in the presence of HA or FA, while Eu(III) interaction with beta-MnO2 was reduced at pH > 6.5 in the presence of HA or FA. The EXAFS fitting results provided a molecular evidence for the findings from the batch experiments. Adsorption of HA or FA onto beta-MnO2 greatly modified the microstructure of Eu(III) onto beta-MnO2. Only binary surface complexes of Eu(III) can be formed onto beta-MnO2 in the absence of HA or FA, while both binary surface complexes and ternary surface complexes of Eu(III) can be simultaneously formed onto beta-MnO2 in the presence of HA or FA, which was mainly responsible for the enhanced Eu(III) uptake at low pH values. The results observed in this work are important for the evaluation of physicochemical behavior of long-lived radionuclides (lanthanides and actinides) in the natural soil and water environment. (C) 2014 Elsevier B.V. All rights reserved.