Calibration and performance of synchronous SIM/scan mode for simultaneous targeted and discovery (non-targeted) analysis of exhaled breath samples from firefighters

•A SIM/Scan method was developed to evaluate target and non-target compounds.•Calibrated the SIM/scan method for eight VOC and eight PAH standards.•Utilized a new dual PAH/VOC standard loading method onto thermal desorption tubes.•Thirty-six firefighter samples were analyzed in SIM/scan mode.•Non-target compounds of interest to exposure were discovered in the scan chromatograms.

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.