Sensitive and Representative Extraction of Petroleum-Based Ignitable Liquids From Fire Debris For Confirmatory Analysis of Canine-Selected Exhibits

Fire debris analysis is focused on the recovery and identification of ignitable liquids to provide context for fire investigation. Investigators use a variety of methods to select suspicious debris for analysis, with ignitable liquid detection canines being one of the most popular. When properly trained and certified, ignitable liquid detection canines offer continuous sampling with high sensitivity and the ability to discriminate between irrelevant and suspicious odours to rapidly locate debris which may contain ignitable liquid residues. However, canine indications are presumptive as they cannot be sufficiently scrutinised by the legal process without confirmatory laboratory analysis. Standard debris analysis methods detect very small amounts of ignitable liquid residue (∼1-0.1 μL) without maximising sensitivity which minimises the risk from false positives and from detection of background petroleum which is ubiquitous in our environment. For canine-selected debris, the goal of the laboratory analysis should be to provide data to confirm or refute the validity of the canine indication. For such confirmatory analysis to be useful, analytical sensitivity should approximate the sensitivity of the canine. The sensitivity of fire debris analysis is most influenced by the selection of the extraction device and tuning of extraction conditions. Non-destructive extractions are preferred for forensic analyses, and solid phase microextraction (SPME) offers an excellent option. However, the original SPME fibres are fragile and tend to skew the chromatographic profile which can lead to high costs and a risk of ignitable liquid misclassification. Herein, we present an optimised SPME extraction method suited to confirmatory analysis of canine-selected exhibits. The method is non-destructive and non-exhaustive, is easily applied to cans of debris, and yields chromatographic profiles equivalent to those obtained by the gold-standard passive headspace sampling (PHS) methods based on activated carbon. Fibre selection, debris temperature, fibre temperature, and extraction time were optimised to yield chromatographic profiles with maximum comparability to reference samples collected as neat liquids or standard PHS extracts. The optimised method is applied to samples recovered from another study which estimated the threshold of the canine’s sensitivity, with the laboratory result compared to the canine result for each sample.