Hamontree Hannah M, Hatcher Patrick G
Department of Chemistry & Biochemistry, Old Dominion University, 4501 Elkhorn Ave, Norfolk, Virginia 23529, United States of America.
J Am Soc Mass Spectrom. 2025 Jun 4;36(6):1377-1385. doi: 10.1021/jasms.5c00077. Epub 2025 May 12.
The emerging risks to organisms of pyrogenic-derived dissolved organic matter (PyDOM) from forest fires are of concern due to its toxic and mutagenic potential (e.g., pro-oxidative responses in fauna through the depletion of glutathione, a nitrogen- and sulfur-containing tripeptide found in cells). This study simulates this phenomenon in a laboratory setting by identifying bonding between reduced l-glutathione and organic molecules in leachates from environmentally weathered biomass samples (charred and uncharred) using Kendrick Mass Defect (KMD) analysis from formula lists obtained from negative-mode electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry ((-)ESI-FT-ICR-MS). These formula lists reveal a 10-fold increase in nitrogen- and sulfur-containing molecular formulas in the charred biomass samples compared with the unreacted charred biomass when subjected to reaction with glutathione. KMD analysis attributed the bonding of glutathione to the biomass leachates accounting for approximately 25% of the new nitrogen- and sulfur-containing molecular formulas as either addition-type or condensation/elimination-type reactions. KMD sheds light on a different fraction of chemically reactive wildfire-produced organic compounds that may be of interest for subsequent toxicological studies.
森林火灾产生的热解衍生溶解有机物（PyDOM）对生物体构成的新风险令人担忧，因为它具有潜在的毒性和致突变性（例如，通过消耗谷胱甘肽，一种细胞中含氮和硫的三肽，对动物产生促氧化反应）。本研究通过使用从负离子模式电喷雾电离-傅里叶变换离子回旋共振质谱（(-)ESI-FT-ICR-MS）获得的分子式列表进行肯德里克质量亏损（KMD）分析，确定环境风化生物质样品（烧焦和未烧焦）渗滤液中还原型L-谷胱甘肽与有机分子之间的键合，从而在实验室环境中模拟这一现象。这些分子式列表显示，与未反应的烧焦生物质相比，烧焦生物质样品中含氮和硫的分子式在与谷胱甘肽反应后增加了10倍。KMD分析将谷胱甘肽与生物质渗滤液的键合归因于约25%的新含氮和硫分子式，这些反应为加成型或缩合/消除型反应。KMD揭示了野火产生的具有化学反应性的有机化合物的不同部分，这些部分可能对后续毒理学研究具有重要意义。
