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

Abstract

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 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 mg/m.

On‐substrate derivatization for detection of highly volatile G‐series chemical warfare agents via paper spray mass spectrometry

“…As noted in previous work, a vapor/aerosol capture device was designed for PS cartridges which forced air through a small region of the whole substrate . Applying varying quantities of a rhodamine B dye solution allows for visualization of spot size per dose quantity (Figure ).…”

“…Developed PS‐based atmospheric sampling devices have proven useful for the capture and direct analysis of CWA G‐series simulants . These devices flow air directly through a substrate, capturing chemistry of interest for subsequent paper spray analysis.…”

“…These devices flow air directly through a substrate, capturing chemistry of interest for subsequent paper spray analysis. G‐series agents have proven difficult to analyze via PS‐MS, due to their short analytical lifetimes before dissipating . Modification of the substrate with MOFs has extended the analytical lifetime to 60 min, enabling the direct detection of the native G‐series agent .…”

Emerging trends in paper spray mass spectrometry: Microsampling, storage, direct analysis, and applications

“…PS MS has been employed for various applications including but not limited to: biomedical and clinical studies (Manicke et al, 2011a; Manicke et al, 2011b; Espy et al, ; Yang et al, ; Shi et al, ; Jeong et al, ; Shi et al, ; Yannell et al, ; Zhang, Glaros, & Manicke, ), illicit drugs (Wiseman & Manicke, ; Manicke, Bills, & Zhang, ; Vega et al, ; Jett, Skaggs, & Manicke, ; Michely, Meyer, & Maurer, ; de Paula et al, ; Liu et al, ; McKenna et al, ), chemical warfare agents (CWAs) (Dhummakupt et al, a; McKenna et al, ), agrochemical analysis (I Pereira, Rodrigues et al, b), environmental and industrial monitoring (Jjunju et al, , ; Maher et al, ), and for studying on‐surface chemical reactions (Yan et al, ; Bag et al, ; Zhou, Pei, & Huang, ; Maher et al, ). PS MS is advantageous in the clinical setting as it provides a means of rapid quantification of drugs and metabolites while minimizing sample preparation steps.…”

Rapid paper spray mass spectrometry characterization of uranium and exemplar molecular species

“…Mass spectrometry has long been recognized as one of the most sensitive methods for the characterization of long‐lived actinides, but these techniques have been used primarily for the quantification of isotopic ratios or the characterization of inorganic contaminants rather than the identification and quantification of specific inorganic complexes. Paper spray ionization mass spectrometry (PSI‐MS) and the closely related swab touch spray ionization mass spectrometry have recently gained attention as versatile, ambient ionization techniques requiring minimal sample preparation and sample consumption for the direct analysis of blood, urine, and environmentally collected chemical warfare agent simulants . In PSI‐MS, the sample is transferred onto a substrate, which is then wetted with solvent while exposed to a high electrical potential to induce electrospray ionization (ESI) directly from the substrate.…”