{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T15:00:53Z","timestamp":1791385253642,"version":"4.3.3"},"reference-count":33,"publisher":"American Chemical Society (ACS)","issue":"10","license":[{"start":{"date-parts":[[2026,8,26]],"date-time":"2026-08-26T00:00:00Z","timestamp":1787702400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-001"},{"start":{"date-parts":[[2026,8,26]],"date-time":"2026-08-26T00:00:00Z","timestamp":1787702400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-009"},{"start":{"date-parts":[[2026,8,26]],"date-time":"2026-08-26T00:00:00Z","timestamp":1787702400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-017"}],"funder":[{"DOI":"10.13039\/100031328","name":"Office of Readiness and Response","doi-asserted-by":"publisher","award":["PID 14972 (FY2021-2022)"],"award-info":[{"award-number":["PID 14972 (FY2021-2022)"]}],"id":[{"id":"10.13039\/100031328","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100031328","name":"Office of Readiness and Response","doi-asserted-by":"publisher","award":["PID 16435 (FY2022-2023)"],"award-info":[{"award-number":["PID 16435 (FY2022-2023)"]}],"id":[{"id":"10.13039\/100031328","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,7]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Exposures to blister agents such as sulfur mustard (HD) have been documented in both military and civilian settings, underscoring the need for reliable clinical assays and biomarkers for confirming human exposure. Accordingly, the Organisation for the Prohibition of Chemical Weapons (OPCW) designates sulfur mustard hydrolysis products (diols) as biomarkers for exposure verification. Because confirmatory analyses in public health and forensic contexts often rely on qualitative identification rather than quantitation alone, we evaluated sensitive qualitative approaches for detecting the diol hydrolysis products of eight of the nine sulfur mustard analogs listed in Schedule 1.A.04 of the Chemical Weapons Convention (CWC) Annex on Chemicals. Human serum spiked with sulfur mustard analogs and plasma and urine spiked with corresponding diols underwent strong base treatment, solid-phase extraction (SPE), derivatization with N-heptafluorobutyrylimidazole (HFBI), and liquid\u2013liquid extraction (LLE). The resulting diol bis-HFB derivatives were analyzed by gas chromatography\u2013triple quadrupole mass spectrometry (GC\u2013QQQ) using electron ionization (EI) and positive chemical ionization (PCI) with methane or ammonia reagent gases. Derivatized diols were detected at concentrations as low as 1.00 ng\/mL across all matrices, with PCI-methane yielding signal-to-noise ratios (S\/N) &amp;gt; 15. Gas chromatography\u2013quadrupole time-of-flight (GC\u2013Q-TOF) analysis provided high-resolution MS and MS\/MS spectra to support molecular formula confirmation of precursor and product ions. By combining EI and PCI with high-resolution mass spectrometry for structural and molecular formula confirmation, this approach enables sensitive, matrix-independent detection, with PCI(CH4) providing the most effective balance between structural information and analytical performance for GC\u2013MS\/MS implementation.<\/jats:p>","DOI":"10.1021\/jasms.6c00197","type":"journal-article","created":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T10:21:32Z","timestamp":1788258092000},"page":"2410-2421","source":"Crossref","is-referenced-by-count":0,"title":["Evaluation of Free\nand Released Sulfur Mustard Diols\nin Human Blood and Urine Using Multi-ionization GC\u2013QQQ and\nGC\u2013Q-TOF"],"prefix":"10.1021","volume":"37","author":[{"ORCID":"https:\/\/orcid.org\/0009-0002-2828-7536","authenticated-orcid":true,"given":"J. Brett","family":"Kimbrell","sequence":"first","affiliation":[{"name":"Centers for Disease Control and Prevention , , , ,","place":["Atlanta, Georgia, United States, 30341"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5477-2052","authenticated-orcid":true,"given":"Brian S.","family":"Crow","sequence":"additional","affiliation":[{"name":"Centers for Disease Control and Prevention , , , ,","place":["Atlanta, Georgia, United States, 30341"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-1706-2418","authenticated-orcid":true,"given":"Thomas B.","family":"Tinkle","sequence":"additional","affiliation":[{"name":"Centers for Disease Control and Prevention , , , ,","place":["Atlanta, Georgia, United States, 30341"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas A.","family":"Blake","sequence":"additional","affiliation":[{"name":"Centers for Disease Control and Prevention , , , ,","place":["Atlanta, Georgia, United States, 30341"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,26]]},"reference":[{"key":"2026100710071738300_cit1","volume-title":"Convention on the Prohibition\nof the Development, Production, Stockpiling and Use of Chemical Weapons\nand on their Destruction","author":"Michael","year":"1992"},{"issue":"6","key":"2026100710071738300_cit2","doi-asserted-by":"publisher","first-page":"254","DOI":"10.1093\/jat\/9.6.254","article-title":"Analysis\nof Thiodiglycol in Urine of Victims of an Alleged Attack with Mustard\nGas","volume":"9","author":"Wils","year":"1985","journal-title":"J. Anal. Toxicol."},{"key":"2026100710071738300_cit3","doi-asserted-by":"publisher","first-page":"184","DOI":"10.1016\/S0378-4347(00)82374-9","article-title":"Quantification\nof\nThiodiglycol in Urine by Electron Ionization Gas Chromatography Mass\nSpectrometry","volume":"528","author":"Jakubowski","year":"1990","journal-title":"J. Chromatogr. B Biomed. Sci.\nAppl."},{"issue":"1\u20132","key":"2026100710071738300_cit4","doi-asserted-by":"publisher","first-page":"177","DOI":"10.1016\/S0021-9673(98)00102-2","article-title":"Analysis of Mustard Hydrolysis Products\nby Packed Capillary Liquid Chromatography\u2013Electrospray Mass\nSpectrometry","volume":"808","author":"D\u2019Agostino","year":"1998","journal-title":"J. Chromatogr. A"},{"issue":"10","key":"2026100710071738300_cit5","doi-asserted-by":"publisher","first-page":"553","DOI":"10.1002\/bms.1200151008","article-title":"Capillary\nColumn Isobutane Chemical Ionization Mass\nSpectrometry of Mustard and Related Compounds","volume":"15","author":"D\u2019Agostino","year":"1988","journal-title":"Biomed. Environ. Mass Spectrom."},{"issue":"2","key":"2026100710071738300_cit6","doi-asserted-by":"publisher","first-page":"405","DOI":"10.1016\/0021-9673(91)80007-4","article-title":"Analysis of 1,1\u2032-Sulphonylbis[2-(Methylsulphinyl)Ethane]\nand 1-Methylsulphinyl-2-[2-(Methylthio)Ethylsulphonyllethane, Metabolites\nof Sulphur Mustard, in Urine Using Gas Chromatography-Mass Spectrometry","volume":"558","author":"Black","year":"1991","journal-title":"J. Chromatogr."},{"issue":"4","key":"2026100710071738300_cit7","doi-asserted-by":"publisher","first-page":"405","DOI":"10.3109\/00498259209046652","article-title":"Biological Fate of Sulphur Mustard,\n1,1\u2019-Thiobis(2-Chloroethane):\nIsolation and Identification of Urinary Metabolites Following Intraperitoneal\nAdministration to Rat","volume":"22","author":"Black","year":"1992","journal-title":"Xenobiotica"},{"key":"2026100710071738300_cit8","doi-asserted-by":"publisher","first-page":"327","DOI":"10.1093\/jat\/28.5.327","article-title":"Quantitation\nof the Sulfur Mustard Metabolites 1,1\u2019-Sulfonylbis[2-(Methylthio)Ethane]\nand Thiodiglycolin Urine Using Isotope-Dilution Gas Chromatography-Tandem\nMass Spectrometry","volume":"28","author":"Boyer","year":"2004","journal-title":"J. Environ. Anal. 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Toxicol."},{"issue":"1","key":"2026100710071738300_cit11","doi-asserted-by":"publisher","first-page":"10","DOI":"10.1093\/jat\/32.1.10","article-title":"Analysis of Urinary Metabolites of\nSulfur Mustard in Two Individuals after Accidental Exposure","volume":"32","author":"Barr","year":"2008","journal-title":"J. Anal. Toxicol."},{"issue":"6","key":"2026100710071738300_cit12","doi-asserted-by":"publisher","first-page":"361","DOI":"10.1002\/(SICI)1099-0461(1998)12:6&lt;361::AID-JBT6&gt;3.0.CO;2-Z","article-title":"In Vitro Oxidation\nof the Hydrolysis Product of Sulfur Mustard, 2,2?-Thiobis-Ethanol,\nby Mammalian Alcohol Dehydrogenase","volume":"12","author":"Brimfield","year":"1998","journal-title":"J. Biochem.\nMol. Toxicol."},{"issue":"5","key":"2026100710071738300_cit13","doi-asserted-by":"publisher","first-page":"244","DOI":"10.1002\/1099-0461(2000)14:5&lt;244::AID-JBT3&gt;3.0.CO;2-4","article-title":"Oxidation of Thiodiglycol (2,2?-Thiobis-Ethanol)\nby Alcohol Dehydrogenase: Comparison of Human Isoenzymes","volume":"14","author":"Dudley","year":"2000","journal-title":"J. Biochem. Mol. Toxicol."},{"issue":"5","key":"2026100710071738300_cit14","doi-asserted-by":"publisher","first-page":"333","DOI":"10.1093\/jat\/28.5.333","article-title":"Retrospective Detection\nof Exposure to Sulfur Mustard:\nImprovements on an Assay for Liquid Chromatography-Tandem Mass Spectrometry\nAnalysis of Albumin\/Sulfur Mustard Adducts","volume":"28","author":"Noort","year":"2004","journal-title":"J. Anal. Toxicol."},{"issue":"2","key":"2026100710071738300_cit15","doi-asserted-by":"publisher","first-page":"256","DOI":"10.1021\/tx500468h","article-title":"Simplified Method\nfor Quantifying Sulfur Mustard Adducts to Blood Proteins by Ultrahigh\nPressure Liquid Chromatography\u2013Isotope Dilution Tandem Mass\nSpectrometry","volume":"28","author":"Pantazides","year":"2015","journal-title":"Chem. Res. Toxicol."},{"issue":"4","key":"2026100710071738300_cit16","doi-asserted-by":"publisher","first-page":"781","DOI":"10.1021\/tx9502148","article-title":"Characterization\nof Sulfur Mustard Induced Structural Modifications in Human Hemoglobin\nby Liquid Chromatography\u2013Tandem Mass Spectrometry","volume":"9","author":"Noort","year":"1996","journal-title":"Chem. Res. Toxicol."},{"issue":"5","key":"2026100710071738300_cit17","doi-asserted-by":"publisher","first-page":"499","DOI":"10.1080\/004982597240460","article-title":"Biological Fate\nof Sulphur Mustard: Identification of Valine and Histidine Adducts\nin Haemoglobin from Casualties of Sulphur Mustard Poisoning","volume":"27","author":"Black","year":"1997","journal-title":"Xenobiotica"},{"issue":"4","key":"2026100710071738300_cit18","doi-asserted-by":"publisher","first-page":"249","DOI":"10.1093\/jat\/21.4.249","article-title":"Verification of Exposure to Sulfur Mustard in Two Casualties\nof the Lran-Lraq Conflict","volume":"21","author":"Benschop","year":"1997","journal-title":"J. Anal. Toxicol."},{"issue":"2","key":"2026100710071738300_cit19","doi-asserted-by":"publisher","first-page":"199","DOI":"10.1021\/tx00038a013","article-title":"Synthesis,\nCharacterization,\nand Quantitation of the Major Adducts Formed between Sulfur Mustard\nand DNA of Calf Thymus and Human Blood","volume":"7","author":"Fidder","year":"1994","journal-title":"Chem.\nRes. Toxicol."},{"key":"2026100710071738300_cit20","doi-asserted-by":"publisher","first-page":"533","DOI":"10.1016\/j.toxrep.2014.07.017","article-title":"Four Sulfur\nMustard Exposure Cases: Overall Analysis of Four Types of Biomarkers\nin Clinical Samples Provides Positive Implication for Early Diagnosis\nand Treatment Monitoring","volume":"1","author":"Xu","year":"2014","journal-title":"Toxicol. 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Pharmacol."},{"issue":"1","key":"2026100710071738300_cit23","doi-asserted-by":"publisher","first-page":"36","DOI":"10.1080\/15563650.2019.1614190","article-title":"Evidence of Sulfur\nMustard Exposure in Victims of Chemical Terrorism by Detection of\nUrinary \u03b2-Lyase Metabolites","volume":"58","author":"Sezigen","year":"2020","journal-title":"Clin. Toxicol."},{"issue":"1","key":"2026100710071738300_cit24","doi-asserted-by":"publisher","first-page":"44","DOI":"10.1093\/jat\/32.1.44","article-title":"Multianalyte Quantification of Five\nSesqui- and Ethyl\nEther Oxy-Mustard Metabolites in Human Urine by Liquid Chromatography-Atmospheric\nPressure Chemical Ionization-Tandem Mass Spectrometry","volume":"32","author":"Ash","year":"2008","journal-title":"J. Anal. Toxicol."},{"issue":"14","key":"2026100710071738300_cit25","doi-asserted-by":"publisher","first-page":"2098","DOI":"10.1021\/ac50008a014","article-title":"Pulsed Positive\nNegative Ion Chemical Ionization Mass Spectrometry","volume":"48","author":"Hunt","year":"1976","journal-title":"Anal. Chem."},{"key":"2026100710071738300_cit26","doi-asserted-by":"publisher","first-page":"261","DOI":"10.1016\/S0021-9673(00)94385-1","article-title":"Detection of Trace Levels of Thiodiglycol in Blood,\nPlasma and Urine Using Gas Chromatography Electron-Capture Negative-Ion\nChemical Ionisation Mass Spectrometry","volume":"449","author":"Black","year":"1988","journal-title":"J. Chromatogr."},{"issue":"2","key":"2026100710071738300_cit27","doi-asserted-by":"publisher","first-page":"283","DOI":"10.1016\/0021-9673(93)83388-9","article-title":"Capillary\nColumn Electron Impact and Ammonia Chemical\nIonization Gas Chromatographic-Mass Spectrometric and Gas Chromatographic-Tandem\nMass Spectrometric Analysis of Mustard Hydrolysis Products","volume":"645","author":"D\u2019Agostino","year":"1993","journal-title":"J. Chromatogr. A"},{"issue":"1\u20132","key":"2026100710071738300_cit28","doi-asserted-by":"publisher","first-page":"157","DOI":"10.1016\/j.chroma.2004.10.039","article-title":"Gas Chromatography\u2013Mass\nSpectrometry Analysis of Trifluoroacetyl Derivatives of Precursors\nof Nitrogen and Sulfur Mustards for Verification of Chemical Weapons\nConvention","volume":"1059","author":"Pardasani","year":"2004","journal-title":"J. Chromatogr. A"},{"issue":"1","key":"2026100710071738300_cit29","doi-asserted-by":"publisher","first-page":"31","DOI":"10.1093\/jat\/32.1.31","article-title":"Improvements in\nthe Methodology of Monitoring Sulfur Mustard Exposure by Gas Chromatography-Mass\nSpectrometry Analysis of Cleaved and Derivatized Blood Protein Adducts","volume":"32","author":"Lawrence","year":"2008","journal-title":"J. Anal. Toxicol."},{"issue":"1","key":"2026100710071738300_cit30","doi-asserted-by":"publisher","first-page":"114","DOI":"10.1016\/j.jchromb.2006.07.065","article-title":"Analysis of the Sulphur Mustard Metabolites\nThiodiglycol and Thiodiglycol Sulfoxide in Urine Using Isotope-Dilution\nGas Chromatography\u2013Ion Trap Tandem Mass Spectrometry","volume":"845","author":"Riches","year":"2007","journal-title":"J. Chromatogr., B"},{"key":"2026100710071738300_cit31","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-319-54398-7","article-title":"Mass Spectrometry:\nA Textbook","volume-title":"Mass Spectrometry","author":"Gross","year":"2017"},{"key":"2026100710071738300_cit32","article-title":"Chemical Ionization\nMass Spectrometry","volume-title":"Chemical Ionization\nMass Spectrometry","author":"Harrison","year":"1992"},{"issue":"8","key":"2026100710071738300_cit33","doi-asserted-by":"publisher","first-page":"1364","DOI":"10.1016\/j.jasms.2007.04.016","article-title":"Mass Spectral Behavior\nof the Hydrolysis Products of Sesqui- and Oxy-Mustard Type Chemical\nWarfare Agents in Atmospheric Pressure Chemical Ionization","volume":"18","author":"Lemire","year":"2007","journal-title":"J. Am. Soc. Mass Spectrom."}],"container-title":["Journal of the American\nSociety for Mass Spectrometry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jasms.6c00197","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jamsef\/article-pdf\/37\/10\/2410\/67419952\/jasms.6c00197.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jamsef\/article-pdf\/37\/10\/2410\/67419952\/jasms.6c00197.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T14:32:29Z","timestamp":1791383549000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jamsef\/article\/37\/10\/2410\/5329766\/Evaluation-of-Free-and-Released-Sulfur-Mustard"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,26]]},"references-count":33,"journal-issue":{"issue":"10","published-online":{"date-parts":[[2026,8,26]]},"published-print":{"date-parts":[[2026,10,7]]}},"URL":"https:\/\/doi.org\/10.1021\/jasms.6c00197","relation":{},"ISSN":["1044-0305","1879-1123"],"issn-type":[{"value":"1044-0305","type":"print"},{"value":"1879-1123","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,26]]}}}