Marine mammals in the past mass mortality events may have been susceptible to infection because their immune systems were suppressed through the bioaccumulation of environmental pollutants such as polychlorinated biphenyls (PCBs). We compiled mortality event data sets of 33 marine mammal species, and employed a Finely-Advanced Transboundary Environmental model (FATE) to model the exposure of the global fish community to PCB congeners, in order to define critical exposure levels (CELs) of PCBs above which mass mortality events are likely to occur. Our modelling approach enabled us to describe the mass mortality events in the context of exposure of higher-trophic consumers to PCBs and to identify marine pollution 'hotspots' such as the Mediterranean Sea and north-western European coasts. We demonstrated that the CELs can be applied to quantify a chemical pollution Planetary Boundary, under which a safe operating space for marine mammals and humanity can exist. © 2014 Elsevier Ltd.