title: Source Attribution of Cyanides Using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics.
abstract: Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock or stock group for a subset of United States stocks resulted in cross-validation errors ranging from 0 to 5.3%.
authors.affiliation: Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States.
authors.forename: Nikhil S
authors.initials: NS
authors.lastname: Mirjankar
authors.affiliation: Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States.
authors.forename: Carlos G
authors.initials: CG
authors.lastname: Fraga
authors.affiliation: Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States.
authors.forename: April J
authors.initials: AJ
authors.lastname: Carman
authors.affiliation: Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States.
authors.forename: James J
authors.initials: JJ
authors.lastname: Moran
mesh_terms: D000838:Anions / Q000737:chemistry; D002247:Carbon Isotopes; D002851:Chromatography, High Pressure Liquid; D016000:Cluster Analysis; D003486:Cyanides / Q000032:analysis* / Q000737:chemistry*; D016002:Discriminant Analysis; D016018:Least-Squares Analysis; D013058:Mass Spectrometry
chemical_list: D000838:Anions; D002247:Carbon Isotopes; D003486:Cyanides