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This article describes the optimization of methodology for extending the measurement of volatile organic compounds (VOCs) to increasingly heavier polycyclic aromatic hydrocarbons (PAHs) with a detailed focus on recent sorbent tube technology. Although PAHs have lower volatility than compounds such as benzene, toluene, ethylbenzene and xylenes, these semi-volatile compounds can be detected in air and breath samples. For this work, PAHs were captured on sorbent tubes and subsequently analyzed using automated thermal desorption gas chromatography - mass spectrometry (ATD-GC/MS). While many different sorbent tubes are commercially available, optimization for airborne PAH sampling using sorbent tubes has not been previously considered. Herein, several commercially available sorbent tubes, including Carbograph 2 TD/1TD, Tenax TA, XRO-440, and inert-coated PAH tubes are compared to determine the relative recovery for eight PAHs commonly found in the environment. Certain types of sorbent materials were found to be better suited for PAH recovery during thermal desorption, and PAH reaction products were observed on several types of sorbent tubes, including graphitized carbon black sorbents with stainless steel tube materials. As such, selection of sorbent tube media should be carefully considered prior to embarking on a PAH study., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Traditionally, gas chromatography-mass spectrometry (GC/MS) analysis has used a targeted approach called selected ion monitoring (SIM) to quantify specific compounds that may have adverse health effects. Due to method limitations and the constraints of preparing duplicate samples, the information that could be obtained from separately collecting the full scan chromatogram of the sample has often been sacrificed. However, the hybrid technique called synchronous SIM/scan mode alternates between the two acquisition modes, maintaining the accuracy and sensitivity of SIM for targeted analysis while also providing the full scan chromatogram for discovery of non-target compounds. This technology was assessed using calibration data and real-world breath samples from a joint EPA/NIOSH collaboration that investigated the safety of firefighters' protective gear during controlled structure burns. Collecting field samples is costly and must be performed strategically to ensure that time points and replicates are accurate and representative of the intended population. This is difficult to accomplish with firefighters who are working under volatile conditions. The synchronous SIM/scan method decreases the number of field samples that need to be collected by half and reduces error in trying to recreate time points since a breath sample from a single sorbent tube can be used to collect both the SIM and scan data simultaneously. As a practical demonstration of the method, we investigate thirty-six firefighter breath samples, document organic compounds of interest, and identify additional non-target compounds., (Published by Elsevier B.V.)