title: Preliminary effects of real-world factors on the recovery and exploitation of forensic impurity profiles of a nerve-agent simulant from office media.
abstract: Dimethyl methylphosphonate (DMMP) was used as a chemical threat agent (CTA) simulant for a first look at the effects of real-world factors on the recovery and exploitation of a CTA's impurity profile for source matching. Four stocks of DMMP having different impurity profiles were disseminated as aerosols onto cotton, painted wall board, and nylon coupons according to a thorough experimental design. The DMMP-exposed coupons were then solvent extracted and analyzed for DMMP impurities by comprehensive 2D gas chromatography/mass spectrometry (GC×GC/MS). The similarities between the coupon DMMP impurity profiles and the known (reference) DMMP profiles were measured by dot products of the coupon profiles and known profiles and by score values obtained from principal component analysis. One stock, with a high impurity-profile selectivity value of 0.9 out of 1, had 100% of its respective coupons correctly classified and no false positives from other coupons. Coupons from the other three stocks with low selectivity values (0.0073, 0.012, and 0.018) could not be sufficiently distinguished from one another for reliable matching to their respective stocks. The results from this work support that: (1) extraction solvents, if not appropriately selected, can have some of the same impurities present in a CTA reducing a CTA's useable impurity profile, (2) low selectivity among a CTA's known impurity profiles will likely make definitive source matching impossible in some real-world conditions, (3) no detrimental chemical-matrix interference was encountered during the analysis of actual office media, (4) a short elapsed time between release and sample storage is advantageous for the recovery of the impurity profile because it minimizes volatilization of forensic impurities, and (5) forensic impurity profiles weighted toward higher volatility impurities are more likely to be altered by volatilization following CTA exposure.
authors.affiliation: Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, WA 99352, USA. carlos.fraga@pnnl.gov
authors.forename: Carlos G
authors.initials: CG
authors.lastname: Fraga
authors.forename: Landon H
authors.initials: LH
authors.lastname: Sego
authors.forename: Jamin C
authors.initials: JC
authors.lastname: Hoggard
authors.forename: Gabriel A Pérez
authors.initials: GA
authors.lastname: Acosta
authors.forename: Emilie A
authors.initials: EA
authors.lastname: Viglino
authors.forename: Jon H
authors.initials: JH
authors.lastname: Wahl
authors.forename: Robert E
authors.initials: RE
authors.lastname: Synovec
mesh_terms: D051337:Chemical Terrorism; D002619:Chemical Warfare Agents / Q000032:analysis* / Q000737:chemistry; D032561:Cotton Fiber; D004784:Environmental Monitoring / Q000379:methods*; D004785:Environmental Pollutants / Q000032:analysis* / Q000737:chemistry; D044707:Forensic Sciences / Q000379:methods*; D008401:Gas Chromatography-Mass Spectrometry; D009757:Nylons / Q000737:chemistry; D009943:Organophosphorus Compounds / Q000032:analysis / Q000737:chemistry
chemical_list: D002619:Chemical Warfare Agents; D004785:Environmental Pollutants; D009757:Nylons; D009943:Organophosphorus Compounds; C031116:dimethyl methylphosphonate