Characterization of a Headspace Sampling Method with a Five Component Diesel Fuel Surrogate

PLOT-cryoadsorption concentrates headspace vapors by sweeping them through porous layer open tubular (PLOT) capillaries chilled to 0 °C to promote adsorption onto an alumina layer. Compared to passive headspace concentration employing activated charcoal strips (ACSs) as adsorbents, PLOT-cryoadsorption has several potential advantages for extracting ignitable liquid (IL) residue from fire debris evidence. Capillary vapor traps can be monitored for breakthrough to avoid problematic displacement that occurs when an adsorbent becomes saturated. Capillaries can also be eluted with acetone to avoid highly toxic carbon disulfide. Future adoption of PLOT-cryoadsorption for fire debris analysis requires investigation of sampling parameters including collection volume, flow rate, and temperature. Here we employ a simple five-component surrogate for diesel fuel (that is, a simulated or artificial diesel fuel) to study the effect of flow rate and sample temperature on the composition and spatial distribution of the collected headspace. Flow rates at or below 1.5 scc (standard cubic centimeters)/min yielded the most repeatable results. Across the range 60 °C to 120 °C, we found that high sample temperatures allowed for the collection of more total analyte and shifted its composition towards lower-volatility components. Consistent with chromatographic theory, higher-volatility components traveled furthest along the length of the capillary and were more prone to breakthrough. We conclude that the surrogate mixture allowed for effective, quantitative comparisons between sampling conditions that could be translated to real diesel fuel.