Advances in Liquid Chromatography for Mustard Agent Exposure Biomonitoring Revealed

In a recent review article published in the journal Analytical and Bioanalytical Chemistry, lead author Valérie Pichon from the Department of Analytical, Bioanalytical Sciences and Miniaturization at ESPCI Paris, PSL University, and Sorbonne Université in Paris, delves into a comprehensive analysis of analytical methods utilizing liquid chromatography for the detection of albumin adducts. These adducts are crucial biomarkers for retrospective biomonitoring of exposure to mustard agents, including sulfur mustard and its analogues (1).

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Mustard agents, also known as mustard gas or sulfur mustard, are a class of chemical warfare agents that were first used extensively during World War I. These agents derive their name from their characteristic mustard-like odor. Mustard agents are blister agents, which means they cause severe skin, eye, and lung damage upon exposure. There are several types of mustard agents, with the most well-known being sulfur mustard (HD) and nitrogen mustard (HN).

The review article aims to provide a comprehensive overview of the analytical procedures developed over the last two decades for the analysis of digested alkylated peptides, which result from the adduction of albumin by various mustard agents. These peptides serve as vital biomarkers, offering a broader window for detecting exposure to chemical agents compared to urine-based biomarkers. Albumin adducts can be detected in the blood or plasma of exposed individuals for up to 25 days after exposure, making them invaluable for assessing exposure over an extended period.

However, the analysis of these digested alkylated peptides presents unique challenges due to the complexity of biological matrices and the often very low concentrations of the target compounds. To overcome these challenges, various sample preparation techniques have been proposed to extract albumin and recover alkylated peptides post-digestion using enzymes. These samples are then subjected to liquid chromatography coupled with mass spectrometry, with or without a derivatization step, for analysis.

The review article provides a comprehensive comparison of the different steps involved in the sample preparation, extraction, and purification of adducted albumin and its digested peptides as described in the literature. The aim is to achieve detection limits in the ng/mL range for biological samples exposed to sulfur mustard, its analogues, and nitrogen mustards. The insights and advances presented in this review not only contribute to the scientific understanding of biomonitoring mustard agent exposure but also have potential implications for improving the safety and well-being of individuals exposed to these hazardous chemicals.

This comprehensive analysis of liquid chromatography-based analytical methods for albumin adduct detection enhances our understanding of exposure biomonitoring, bringing us closer to more effective tools for evaluating and mitigating the risks associated with mustard agent exposure.

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Reference

(1) Pichon, V.; et al. Analytical Methods Based on Liquid Chromatography for the Analysis of Albumin Adducts Involved in Retrospective Biomonitoring of Exposure to Mustard Agents. Anal. Bioanal. Chem. 2023, 1-16. DOI: 10.1007/s00216-023-04925-y