Laser assisted sampling vs direct desorption flowing atmospheric pressure afterglow mass spectrometry of complex polymer samples: Forensic implications for pressure sensitive tape chemical analysis.

Flowing atmospheric pressure afterglow (FAPA) mass spectrometry (MS) is an easy-to-use, cost-effective, and potentially portable technique that allows direct desorption/ionization from samples with little-to-no sample preparation for real-time chemical analysis. However, it has limitations regarding analytes with low desorption efficiency, such as polymers. Here, laser assisted sampling (LAS) is developed and coupled to FAPA MS to allow access to a wider range of chemical information from polymer samples. This is achieved through laser-induced pyrolysis conditions that provide a much higher degree of spatio-temporal control compared to typical pyrolysis techniques. LAS FAPA MS, together with direct desorption FAPA MS, is implemented on pressure sensitive adhesive (PSA) tape samples, which are often found at crime scenes and recovered as forensic evidence. Comparative PSA tape examination is typically performed to assess any differences in the comparison of unknown and known samples and provide an evidentiary association between suspects and crime scenes in forensic applications. PSA tape samples from several manufacturers of duct, masking, and electrical tape were analyzed from the adhesive and backing side. Direct desorption FAPA provides top-surface selectivity and the tape mass spectra are dominated by more peaks at lower m/z, many of which correspond to polymer additives. LAS gives access to sampling from all of the tape layers and the FAPA mass spectra is extended to higher m/z, while polymer fragmentation patterns are evident. Principal components analysis (PCA) was implemented to assess the ability of each technique to distinguish and categorize identified tape classes within the sampled population. The complementary nature of the resulting mass spectra from direct desorption vs LAS FAPA was evident from the PCA as different tape brands sub-sets were discriminated by each technique. The differentiation obtained by combining both methods is already competitive, or better, than conventional techniques, with the additional benefits of AMS.