Background: First responders (i.e., paramedics and firefighters) are exposed to several hazardous chemicals in their work environment such as polycyclic aromatic hydrocarbons (PAHs). Despite periodic self-reporting of exposures during emergency incident response, methods to document objective chemical exposures are limited. We pilot tested the use of silicone-based wristbands as a personal sampling device for chemical exposures in the first responder work environment. Methods: Silicone-based wristbands were cleaned via a standardized protocol developed in our laboratories to remove contaminants from the silicone surface for adsorption. The wristbands were deployed for a 24-hour data collection period in three experimental test conditions: 1) pelican cases containing first responder gear that was exposed to fire [n=8 wristbands]; 2) pelican cases containing gear not recently exposed to fire [n=4]; and 3) various communal areas of the fire station (i.e., bunks, kitchen, bay area) [n=9]. The bands subsequently underwent chemical extraction and characterization using gas chromatography-mass spectrometry (GC-MS). Results: Wristbands placed in the pelican cases with firefighter safety gear that had been exposed to a fire incident recently contained the following PAHs: Naphthalene, Acenaphthylene, Phenanthrene, 1-Methyl, 2-Methyl, Acenaphene, Flourene, Anthracene, and Pyrene. Wristbands placed in the pelican cases with firefighter safety gear that was not exposed to fire recently contained: Napthalene, 1-Methyl, 2-Methyl, Acenaphthylene, Flourene, and Phenanthrene. Wristbands placed around the fire station's communal areas had 1-Methylnaphthalene, 2-Methylnaphthalene, Acenaphthylene, Anthracene, and Phenanthrene present. Control wristbands, not exposed to anything, didn’t contain any PAHs of interest from GC-MS libraries. Conclusions: PAHs were present in various locations in the first responder work environment and off-gassed from their safety gear. We demonstrated that our silicone-based wristbands serve as a feasible, inexpensive and non-invasive method to objectively characterize chemical exposures in the work environment.