ABSTRACT
Trace evidence, including hair, fibers, soil/dust, and gunshot residue (GSR), can be recovered from a crime scene to help identify or associate a suspect with illegal activities via physical, chemical, and biological testing. Vacuum collection is one technique that is employed in recovering such trace evidence but is often done so in a targeted manner, leaving other complementary, chemical-specific information unexamined. Here, we describe a modified 3D-printed cone spray ionization (3D-PCSI) source with integrated vacuum collection for on-site, forensic evidence screening, allowing the processing of targeted physical traces and nontargeted chemical species alike. The reported form factor allows sample collection, onboard extraction, filtration, and spray-based ionization in a singular vessel with minimal handling of evidence by the operator. Utilizing authentic forensic evidence types and portable MS instrumentation, this new method was characterized through systematic studies that replicate CSI applications. Reliability in the form of false positive/negative response rates was determined from a modest, user-blinded data set, and other attributes, such as collection efficacy and detection limit, were examined.
ABSTRACT
RATIONALE: The burgeoning concern of N-nitrosamine (NAM) contamination found in various pharmaceutical compositions has increased the demand for rapid and reliable screening methods to better assess the breadth of the problem. These carcinogenic compounds are also found in food, water, and soil, and they have been used in poison-related homicides. METHODS: A combination of complementary, ambient ionization methods, paper spray ionization (PSI) and filter cone spray ionization (FCSI)-mass spectrometry (MS), was characterized towards trace-level residue screening of select NAMs (e.g., N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodibutylamine) directly from complex and problematic matrices of interest, including prescription and over-the-counter tablets, drinking water, soil, and consumable goods. Spectral data for analyte confirmation and detection limit studies were collected using a Thermo LCQ Fleet ion trap mass spectrometer. RESULTS: PSI-MS and FCSI-MS readily produced mass spectral data marked by their simplicity (e.g., predominantly protonated molecular ions observed) and congruence with traditional electrospray ionization mass spectra in under 2 min. per sample. Both methods proved robust to the complex matrices tested, yielding ion signatures for target NAMs, as well as active pharmaceutical ingredients for analyzed tablets, flavorants inherent to food products, etc. Low part-per-million detection limits were observed but were shown dependent on sample composition. CONCLUSIONS: PSI-MS and FCSI-MS were successful in detecting trace-level NAMS in complex liquid- and solid-phase matrices with little to no prior preparation. This work suggests that these methodologies can provide a means for assessing problematic pharmaceutical adulterants/degradants for expedited quality control, as well as enhancing environmental stewardship efforts and forensic investigations.
