Polycyclic musks (PCMs) are synthetic fragrance compounds used in personal care products and household cleaners. Previous studies have indicated that PCMs are introduced to aquatic environments via wastewater and river discharge. Polyethylene passive samplers (PEs) were deployed in air and water during winter 2011 and summer 2012 to investigate the role of population centers as sources of these contaminants to the Great Lakes and determine whether the lakes were acting as sources of PCMs via volatilization. Average gaseous Σ5PCM ranged from below detection limits (3 on the western shoreline of Lake Erie in Toledo. Average dissolved Σ5PCM ranged from 5PCM in both air and water, with strongest correlations within a 25 and 40 km radius, respectively. At sites where HHCB was detected it was generally volatilizing, while the direction of AHTN air-water exchange was variable. Volatilization fluxes of HHCB ranged from 11 ± 6 to 341 ± 127 ng/m2/day, while air-water exchange fluxes of AHTN ranged from -3 ± 2 to 28 ± 10 ng/m2/day. Extrapolation of average air-water exchange flux values over the surface area of the lakes' coastal boundary zone suggested volatilization may be responsible for the loss of 64-213 kg/year of dissolved Σ5PCM from the lakes.