Systematic Revealing of Plant-Derived Nerve Agent Exposure Markers by In-Source Fragmentation-Enabled HRMS...

Area of Science:

• Environmental Science
• Forensic Chemistry
• Analytical Chemistry

Background:

• Identifying diverse, uncharacterized plant-derived nerve agent adducts presents a significant challenge for environmental exposure confirmation and forensic attribution.
• Existing methods struggle to comprehensively detect and characterize these complex compounds in environmental matrices.

Purpose of the Study:

• To develop and validate a novel screening strategy for identifying diverse, uncharacterized plant-derived nerve agent adducts.
• To establish an expansive repository of previously unreported candidate markers for nerve agent exposure.

Main Methods:

• A fragmentation pattern-driven, nontargeted screening strategy was developed, integrating in-source fragmentation with Full MS, all-ion fragmentation (AIF), and neutral loss (NL)-triggered ddMS2 acquisition.
• Agent-specific neutral losses and diagnostic fragment ions were utilized to identify adduct-related features.
• High-resolution MS data, fragmentation pathways, and density functional theory calculations were employed for structural elucidation.

Main Results:

• 256 tentative adduct-related features were identified across four nerve agents and four plant species.
• Structural characteristics and preferential adduction sites were elucidated.
• Nine features showed conservation across plant species, and 11 were detectable at low exposure levels in Arabidopsis thaliana.

Conclusions:

• The developed strategy significantly expands the detectable chemical space for plant-derived nerve agent adducts.
• The findings provide a transferable framework for environmental exposure assessment and emerging contaminants research.
• The identified features hold potential as viable markers for nerve agent exposure confirmation and attribution.