Direct Analysis of Aerosolized Chemical Warfare Simulants Captured on a Modified Glass-Based Substrate by “Paper-Spray” Ionization

• Published in: Analytical chemistry (Washington) 2017-10, Vol.89 (20), p.10866-10872
• Main Authors: Dhummakupt, Elizabeth S, Mach, Phillip M, Carmany, Daniel, Demond, Paul S, Moran, Theodore S, Connell, Theresa, Wylie, Harold S, Manicke, Nicholas E, Nilles, J. Michael, Glaros, Trevor
• Format: Article
• Language: English
• Subjects: Aerosols; Air flow; Ammonium; Ammonium sulfate; Analytical chemistry; Cartridges; Chemical compounds; Chemical warfare; Chemistry; Efficiency; Fiberglass; Filters; Glass fibers; Glass substrates; Ionization; Mass spectrometry; Mass spectroscopy; Phosphates; Sample preparation; Sulfates; Three dimensional printing
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.7b02530

Paper spray ionization mass spectrometry offers a rapid alternative platform requiring no sample preparation. Aerosolized chemical warfare agent (CWA) simulants trimethyl phosphate, dimethyl methylphosphonate, and diisopropyl methylphosphonate were captured by passing air through a glass fiber filter disk within a disposable paper spray cartridge. CWA simulants were aerosolized at varying concentrations using an in-house built aerosol chamber. A custom 3D-printed holder was designed and built to facilitate the aerosol capture onto the paper spray cartridges. The air flow through each of the collection devices was maintained equally to ensure the same volume of air sampled across methods. Each approach yielded linear calibration curves with R 2 values between 0.98–0.99 for each compound and similar limits of detection in terms of disbursed aerosol concentration. While the glass fiber filter disk has a higher capture efficiency (≈40%), the paper spray method produces analogous results even with a lower capture efficiency (≈1%). Improvements were made to include glass fiber filters as the substrate within the paper spray cartridge consumable. Glass fiber filters were then treated with ammonium sulfate to decrease chemical interaction with the simulants. This allowed for improved direct aerosol capture efficiency (>40%). Ultimately, the limits of detection were reduced to levels comparable to current worker population limits of 1 × 10–6 mg/m3.