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Examination of Firearms Review: 2007 to 2010 - Interpol

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3.3.4 Chemical warfare agents<br />

Organophosphorus nerve agents and sulphur or nitrogen mustard are among<br />

the most <strong>to</strong>xic organic compounds used as chemical warfare agents by both<br />

military and terrorists. An overview <strong>of</strong> biological markers <strong>of</strong> exposure <strong>to</strong><br />

chemical warfare agents was reported; metabolites, protein, and/or DNA<br />

adducts were identified for most nerve agents and vesicants, and validated in<br />

experimental animals or in a small number <strong>of</strong> human exposures [345].<br />

An analytical method for determining the metabolic hydrolysis products <strong>of</strong><br />

organophosphorus nerve agents, such as sarin (GB) and cyclosarin (GF), has<br />

been developed using LC-ESI-TOFMS, with an LOD <strong>of</strong> 2 ng/mL in plasma<br />

[346], and HILIC-MS/MS down <strong>to</strong> LOQ <strong>of</strong> 1 ng/mL in human urine [347]. The<br />

biomarker ethyl methylphosphon<strong>of</strong>luoridate (VX-G) <strong>of</strong> VX was measured in red<br />

blood cells (RBC) following treatment with fluoride ion using iso<strong>to</strong>pe-dilution<br />

GC-MS/MS, with an absolute detection limit <strong>of</strong> < 1 pg on column [348]. The<br />

method was used for analysis <strong>of</strong> minipig RBC samples following exposure <strong>to</strong><br />

VX vapor [349,350], and concluded that VX-G was a more precise indica<strong>to</strong>r for<br />

severity <strong>of</strong> exposure than analysis <strong>of</strong> acetylcholinesterase (AChE) inhibition<br />

[349].<br />

Four methods were used <strong>to</strong> moni<strong>to</strong>r the reaction <strong>of</strong> albumin with soman:<br />

Progressive inhibition <strong>of</strong> the aryl acylamidase activity <strong>of</strong> albumin, the release <strong>of</strong><br />

fluoride ion from soman, 31 P NMR, and MS. The study concluded that<br />

soman-albumin adducts detected by MS was useful for the diagnosis <strong>of</strong> soman<br />

exposure [351]. A fluoride ion-based regeneration assay with iso<strong>to</strong>pe dilution,<br />

followed by large volume injection GC-CI-MS, was developed for the detection<br />

<strong>of</strong> soman in rat plasma. With the use <strong>of</strong> an iso<strong>to</strong>pe labeled internal standard,<br />

the LOD was 5.65 pg (on column) with an average recovery <strong>of</strong> 93% [352].<br />

Nanoparticle-based electrochemical immunosensor provides an opportunity <strong>to</strong><br />

develop field-deployable, sensitive, and quantitative biosensors for moni<strong>to</strong>ring<br />

exposure <strong>to</strong> a variety <strong>of</strong> OP pesticides and nerve agents, by the detection <strong>of</strong><br />

the potential marker phosphorylated acetylcholinesterase (Phospho-AChE).<br />

Experimental results showed that the developed electrochemical quartz crystal<br />

microbalance technique can allow the detection <strong>of</strong> Phospho-AChE in human<br />

plasma, with a detection limit <strong>of</strong> 0.020 nM-8.0 pM [353,354]. The AChE<br />

enzyme activity was investigated using a carbon nanotube-based<br />

655

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