A supported catalyst composed by the active phase Rh/Ce0.9Pr0.1O2 loaded on gamma-Al2O3 particles was prepared and characterised by SEM, TEM, XRD, Raman spectroscopy, N-2 adsorption at -196 degrees C, H-2-TPR and XPS. The catalytic decomposition of N2O was studied in simulated nitric acid plant streams (in the presence of O-2, H2O and/or NOx) both in a fix-bed reactor and by in situ DRIFTS-MS experiments. The supported catalyst is able to decompose N2O from around 350-400 degrees C in the presence of O-2, H2O and/or NOx, and this temperature would be enough to decompose N2O in a nitric acid production plant after the expansion turbine, avoiding the use of an additional energy input. Among O-2, H2O and NOx, NOx is the strongest inhibitor and O-2 the weakest. The inhibiting effect of O-2 is attributed to its reversible chemisorption on catalyst active sites, while the effect of H2O and NOx is mainly related with their irreversible chemisorption. The inhibition of H2O is not as high as that of NOx because the product of H2O chemisorption (Ce-OH surface groups) is suitable for N2O chemisorption and decomposition, while the surface nitrogen species created upon NOx chemisorption are not. (c) 2012 Elsevier Ltd. All rights reserved.