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The variety of increasingly complex powertrains including Plug-In Hybrid Electric Vehicles (PHEVs) is associated with a number of challenges to measure exhaust gas emissions: Although the conventional constant volume sampling (CVS) and exhaust gas measurement systems remain a high precision emission measurement concept new questions occur that need to be answered, such as mass transport, catalyst cooling during ICE-off and emission measurement accuracy. Mass transport of exhaust emissions from the transfer tube into the dilution tunnel during engine-off complicates phase assignment. This includes the investigation of the physical processes that are diffusion on basis of concentration differences, extraction due to the CVS underpressure and convection because of density diversities. Catalyst cooling will be investigated using a temperature sensor positioned at the oxy catalyst of a Diesel-PHEV.