Abundance-based model evaluations with observations provide critical tests for the simulated mean state in models of intercontinental pollution transport, and under certain conditions may also offer constraints on model responses to emission changes. We compile multi-year measurements of peroxyacetyl nitrate (PAN) available from five mountaintop sites and apply them in a proof of concept approach that exploits an ensemble of global chemical transport models (HTAP1) to identify an observational “emergent constraint”. In April, when the signal from anthropogenic emissions on PAN is strongest, simulated PAN at northern mid-latitude mountaintops correlates strongly with PAN source-recept relationships (the response to 20% reductions in precursor emissions within northern mid-latitude continents; hereafter, SRRs). This finding implies that PAN measurements can provide constraints on PAN SRRs by limiting the SRR range to that spanned by the subset of models simulating PAN within the observed range. In some cases, regional anthropogenic volatile organic compound (AVOC) emissions, tracers of transport from different source regions, and SRRs for ozone also correlate with PAN SRRs. Given the large observed interannual variability in the limited available datasets, establishing strong constraints will require matching meteorology in the models to the PAN measurements. Application of this evaluation approach to the chemistry-climate models used to project changes in atmospheric composition will require routine, long-term mountaintop PAN measurements to discern both the climatological SRR signal and its inter-annual variability.