For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant ((NO)-N-15) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and PURh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H-2 and/or CO and NO on reduced Rh and/or Pt sites. The second N-2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O-2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H-2. The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 degrees C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 degrees C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 degrees C even when CO was used as a reductant. (C) 2007 Elsevier B.V. All rights reserved.