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A challenge in environmental passive sampling is determining when equilibrium is achieved between the sampler, target contaminants, and environmental phases. A common approach is the use of performance reference compounds (PRCs) to estimate target contaminant sampling rates and indicate degree of sampler equilibrium. One logistical issue associated with using PRCs is their sometimes exorbitant cost. To address PRC expense, this investigation 1) compared the performance of inexpensive PRCs (deuterated PAHs) and expensive PRCs (C-13-labeled PCBs) to estimate dissolved PCB concentrations in freshwater and marine deployments, and 2) evaluated the use of smaller quantities of PRC relative to regular amounts used for estimating dissolved PAH and PCB concentrations. Saltwater and freshwater site average differences between total dissolved PCB concentrations calculated using the 2 classes of PRCs was 34 pg/L (20%) and 340 pg/L (51%), respectively, and in some deployments, statistical differences in PCB concentrations generated by the 2 types of PRCs were detected. However, no statistical differences were detected between total dissolved PAH and PCB for the 3 quantities of PRCs. In both investigations, individual dissolved PCB congeners and PAH compounds demonstrated comparable behavior as those expressed as total PCB or PAH dissolved concentrations. This research provides evidence that in some applications passive sampling using inexpensive and smaller quantities of PRCs can yield cost savings of approximately 75%. This approach appears most promising in the marine water column and when focusing on dissolved concentrations of low and medium molecular weight congeners or total PCBs. Published 2014 SETAC. This article is a US Government work and, as such, is in the public domain in the USA.