The effects of atmospheric CO2 on surface segregation and phase formation in La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF-6428) were investigated. (0 0 1)-oriented LSCF-6428 thin films were deposited on lattice matched (1 1 0)-oriented NdGaO3 (NGO) substrates by pulsed laser deposition (PLD). Using the synchrotron technique of total reflection X-ray fluorescence (TXRF), it was found that the kinetics of Sr surface segregation was enhanced when annealing at 800 degrees C in a high-CO2 partial pressure, as compared to a similar anneal in a CO2-free atmosphere, with the oxygen partial pressure being constant in both cases. Hard X-ray photoelectron spectroscopy (HAXPES) measurements showed that the contribution of the surface carbonate to surface oxide phases increased significantly for the sample annealed in the high-CO2 atmosphere. Atomic force microscopy (AFM) studies showed enhanced surface phase formation during the high-CO2 partial pressure anneal. Density functional theory (DFT) calculations provide a thermodynamic basis for the enhanced kinetics of surface segregation in the presence of atmospheric CO2. (C) 2014 Elsevier B.V. All rights reserved.