The influence of U(VI)-CO3 and Ca-U(VI)-CO3 complexes on U(VI) adsorption onto red soil and nanoscale zero-valent iron (NZVI) was investigated using batch adsorption and fixed-bed column experiments to simulate the feasibility of NZVI as the reactive medium in permeable- reactive barriers (PRB) for in situ remediation of uranium-contaminated red soils. The adsorption capacity (q(e)) and distribution constant (K-d) of NZVI and red soil decreased with increasing pH, dissolved carbonate and calcium concentrations, but the q(e) and K-d values of NZVI were 5-10 times higher than those of red soil. The breakthrough pore volume (PV) values increased with the decrease of pH, dissolved carbonate and calcium concentration; however, the breakthrough PV values of the PRB column filled with 5% NZVI were 2.0-3.5 times higher than the 100% red soil column. The U(VI)-CO3 complexes adsorbed onto the surface of red soil/NZVI ( SOH) to form SO-UO2CO3- or SO-UO2 (CO3)(2)(3-). XPS and XRD analysis further confirmed the reduction of U(VI) to U(IV) and the formation of FeOOH on NZVI surfaces. The findings of this study are significant to the remediation of uranium-contaminated red soils and the consideration of practical U(VI) species in the natural environment. (C) 2015 Elsevier B.V. All rights reserved.