A system and method for controlling an aftertreatment assembly includes a diesel oxidation catalyst (DOC) device configured to receive an exhaust gas. One or more sensors are configured to obtain respective sensor data relative to the exhaust gas and DOC device. A controller is in communication with the sensors and configured to obtain respective sensor data relative to the exhaust gas. The controller is configured to determine if one or more enabling conditions are met, including reaching a predefined temperature range in the DOC device. A rich event is induced targeting a predetermined range of a lambda value for a predefined maximum time duration. When the rich event has ended, an exotherm index is obtained for an observation window immediately after the rich event. The controller is configured to control operation of the aftertreatment assembly based at least partially on the exotherm index.