{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T14:53:19Z","timestamp":1785941599816,"version":"3.56.0"},"reference-count":38,"publisher":"American Chemical Society (ACS)","issue":"8","license":[{"start":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T00:00:00Z","timestamp":1783900800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T00:00:00Z","timestamp":1783900800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T00:00:00Z","timestamp":1783900800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001665","name":"Agence Nationale de la Recherche","doi-asserted-by":"publisher","award":["ANR-11-INBS-0010"],"award-info":[{"award-number":["ANR-11-INBS-0010"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100006021","name":"Direction G?n?rale de l?Armement","doi-asserted-by":"publisher","award":["22470120"],"award-info":[{"award-number":["22470120"]}],"id":[{"id":"10.13039\/501100006021","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100018833","name":"Agence de l'innovation de D?fense","doi-asserted-by":"publisher","award":["2022 65 0036"],"award-info":[{"award-number":["2022 65 0036"]}],"id":[{"id":"10.13039\/501100018833","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,5]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>In chemical forensics, chemical source inference is crucial for the determination of the origin of toxic agents through various analytical and chemometric methodologies. Recent advancements in the study of organophosphorus compounds as nerve agents have mainly focused on the identification of specific production pathways and source materials. Using Chlorpyrifos as a model organophosphorus compound and previously generated data, the present work aims to assess the robustness of the approach for the discrimination of chemical production routes by introducing environmental matrix complexity. Various crude Chlorpyrifos synthesis samples were spiked onto three complex environmental matrices (sand, soil, and surface river water) to simulate real-case samples. Experiments were carried out at two concentrations (20 ng\/\u03bcL and 1 ng\/\u03bcL) in crude samples. Sampling and extraction protocols were developed, and recovery rates and matrix effects were assessed to track down impurity attribution signatures linked to the synthetic pathways from each matrix. Ultra-high-performance liquid chromatography (UHPLC) coupled to a hybrid trapped ion mobility-quadrupole time-of-flight system (TIMS-Q-ToF) was used in a metabolomics-based analytical strategy. Synthetic routes for contaminated environmental samples were predicted using a training data set from various raw Chlorpyrifos synthetic pathways. Precision and the number of discriminant features in samples from Non-Targeted Analysis (NTA) versus Suspect Screening Analysis (SSA) approaches were evaluated with confusion matrices and univariate analysis to assess the relevance of the features employed. Finally, highly concentrated explosive residues were added to evaluate analytical perturbance. This application in complex environmental conditions represents a key step toward validating the proof of concept\u2019s transferability and exploring its analytical limitations.<\/jats:p>","DOI":"10.1021\/jasms.6c00112","type":"journal-article","created":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T10:43:04Z","timestamp":1783939384000},"page":"1848-1857","source":"Crossref","is-referenced-by-count":0,"title":["Nontargeted LC-HRMS-Based\nStrategies as a Tool to\nStudy the Behavior of Chemical Attribution Signatures of Organophosphorus\nin Complex Environmental Matrices"],"prefix":"10.1021","volume":"37","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6550-5972","authenticated-orcid":true,"given":"Carla","family":"Orlandi","sequence":"first","affiliation":[{"name":"Univ Toulouse , , ,","place":["Toulouse, France, F-31027"]},{"name":"MetaboHUB-Metatoul , , ,","place":["Toulouse, France, F-31027"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gre\u0301goire","family":"Delaporte","sequence":"additional","affiliation":[{"name":"DGA CBRN Defence , , 5 Rue Lavoisier , ,","place":["Vert-le-Petit, France, F-91710"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christine","family":"Albaret","sequence":"additional","affiliation":[{"name":"DGA CBRN Defence , , 5 Rue Lavoisier , ,","place":["Vert-le-Petit, France, F-91710"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marie","family":"Tremblay-Franco","sequence":"additional","affiliation":[{"name":"Univ Toulouse , , ,","place":["Toulouse, France, F-31027"]},{"name":"MetaboHUB-Metatoul , , ,","place":["Toulouse, France, F-31027"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Emmanuel","family":"Joubert","sequence":"additional","affiliation":[{"name":"DGA CBRN Defence , , 5 Rue Lavoisier , ,","place":["Vert-le-Petit, France, F-91710"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anne","family":"Bosse\u0301e","sequence":"additional","affiliation":[{"name":"DGA CBRN Defence , , 5 Rue Lavoisier , ,","place":["Vert-le-Petit, France, F-91710"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3600-0902","authenticated-orcid":true,"given":"Laurent","family":"Debrauwer","sequence":"additional","affiliation":[{"name":"Univ Toulouse , , ,","place":["Toulouse, France, F-31027"]},{"name":"MetaboHUB-Metatoul , , ,","place":["Toulouse, France, F-31027"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4568-9177","authenticated-orcid":true,"given":"Emilien L.","family":"Jamin","sequence":"additional","affiliation":[{"name":"Univ Toulouse , , ,","place":["Toulouse, France, F-31027"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,13]]},"reference":[{"key":"2026080510105737500_cit1","doi-asserted-by":"publisher","first-page":"334","DOI":"10.1007\/s11419-021-00578-7","article-title":"Recent Progress\nin the Chemical Attribution of Chemical Warfare Agents and Highly\nToxic Organophosphorus Pesticides","volume":"39","author":"Lu","year":"2021","journal-title":"Forensic\nToxicol."},{"key":"2026080510105737500_cit2","doi-asserted-by":"publisher","first-page":"120753","DOI":"10.1016\/j.talanta.2020.120753","article-title":"The Identification of Chemical Attribution\nSignatures of Stored VX Nerve Agents Using NMR, GC-MS, and LC-HRMS","volume":"211","author":"Ovenden","year":"2020","journal-title":"Talanta"},{"key":"2026080510105737500_cit3","doi-asserted-by":"publisher","first-page":"123890","DOI":"10.1016\/j.talanta.2022.123890","article-title":"Forensic\nAnalysis of the Deuterium\/Hydrogen Isotopic Ratios of the Nerve Agent\nSarin, Its Reaction by-Product Diisopropyl Methylphosphonate and Their\nPrecursors by 2H SNIF-NMR","volume":"253","author":"Meier","year":"2023","journal-title":"Talanta"},{"issue":"36","key":"2026080510105737500_cit4","doi-asserted-by":"publisher","first-page":"12230","DOI":"10.1021\/acs.analchem.1c01271","article-title":"Source Attribution of the Chemical\nWarfare Agent Soman\nUsing Position-Specific Isotope Analysis by 2H NMR Spectroscopy: From\nPrecursor to Degradation Product","volume":"93","author":"Lindberg","year":"2021","journal-title":"Anal. Chem."},{"key":"2026080510105737500_cit5","doi-asserted-by":"publisher","first-page":"586","DOI":"10.1016\/j.talanta.2018.02.104","article-title":"Part 1: Tracing Russian\nVX to Its Synthetic Routes by Multivariate Statistics of Chemical\nAttribution Signatures","volume":"186","author":"Ho\u0308jer Holmgren","year":"2018","journal-title":"Talanta"},{"key":"2026080510105737500_cit6","doi-asserted-by":"publisher","first-page":"269","DOI":"10.1016\/j.chroma.2012.10.053","article-title":"Preliminary\nEffects of Real-World\nFactors on the Recovery and Exploitation of Forensic Impurity Profiles\nof a Nerve-Agent Simulant from Office Media","volume":"1270","author":"Fraga","year":"2012","journal-title":"J. Chromatogr. A"},{"key":"2026080510105737500_cit7","doi-asserted-by":"publisher","first-page":"615","DOI":"10.1016\/j.talanta.2018.02.100","article-title":"Synthesis Route Attribution of Sulfur Mustard by Multivariate\nData Analysis of Chemical Signatures","volume":"186","author":"Ho\u0308jer Holmgren","year":"2018","journal-title":"Talanta"},{"issue":"10","key":"2026080510105737500_cit8","doi-asserted-by":"publisher","first-page":"5406","DOI":"10.1021\/acs.analchem.6b00766","article-title":"Organic Chemical\nAttribution Signatures for the Sourcing of a Mustard Agent and Its\nStarting Materials","volume":"88","author":"Fraga","year":"2016","journal-title":"Anal. Chem."},{"key":"2026080510105737500_cit9","doi-asserted-by":"publisher","first-page":"100473","DOI":"10.1016\/j.forc.2023.100473","article-title":"Interlaboratory Comparison\nStudy of a Chemical Profiling Method for Methylphosphonic Dichloride,\na Nerve Agent Precursor","volume":"33","author":"Ho\u0308jer Holmgren","year":"2023","journal-title":"Forensic Chem."},{"key":"2026080510105737500_cit10","doi-asserted-by":"publisher","first-page":"155","DOI":"10.1016\/j.chroma.2014.06.100","article-title":"Comparative Evaluation of Preprocessing\nFreeware on\nChromatography\/Mass Spectrometry Data for Signature Discovery","volume":"1358","author":"Coble","year":"2014","journal-title":"J. Chromatogr. 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Chem."},{"key":"2026080510105737500_cit13","doi-asserted-by":"publisher","first-page":"116320","DOI":"10.1016\/j.ijms.2020.116320","article-title":"Direct Detection of\nChemical Warfare Agent Simulants in Soil by Thermal\nDesorption-Low Temperature Plasma-Mass Spectrometry","volume":"451","author":"Li","year":"2020","journal-title":"Int. J. Mass Spectrom."},{"issue":"2","key":"2026080510105737500_cit14","doi-asserted-by":"publisher","first-page":"142","DOI":"10.1039\/D2AY01650H","article-title":"Verification of Exposure to Chemical\nWarfare Agents through Analysis of Persistent Biomarkers in Plants","volume":"15","author":"de Bruin-Hoege\u0301e","year":"2023","journal-title":"Anal. 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Chem."},{"key":"2026080510105737500_cit19","doi-asserted-by":"publisher","first-page":"10","DOI":"10.1016\/j.trac.2016.06.002","article-title":"Ion Mobility\nSpectrometry: Current Status and Application\nfor Chemical Warfare Agents Detection","volume":"85","author":"Puton","year":"2016","journal-title":"TrAC,\nTrends Anal. Chem."},{"key":"2026080510105737500_cit20","doi-asserted-by":"publisher","first-page":"92","DOI":"10.1016\/j.talanta.2016.11.016","article-title":"Evaluating and Modeling\nthe Effects\nof Surface Sampling Factors on the Recovery of Organic Chemical Attribution\nSignatures Using the Accelerated Diffusion Sampler and Solvent Extraction","volume":"164","author":"Mo","year":"2017","journal-title":"Talanta"},{"key":"2026080510105737500_cit21","doi-asserted-by":"publisher","first-page":"597","DOI":"10.1016\/j.talanta.2018.02.103","article-title":"Part 2: Forensic\nAttribution Profiling of Russian VX in Food Using Liquid Chromatography-Mass\nSpectrometry","volume":"186","author":"Jansson","year":"2018","journal-title":"Talanta"},{"issue":"11","key":"2026080510105737500_cit22","doi-asserted-by":"publisher","first-page":"4850","DOI":"10.1021\/acs.analchem.0c04555","article-title":"Route Determination\nof Sulfur Mustard Using Nontargeted Chemical Attribution Signature\nScreening","volume":"93","author":"Ho\u0308jer Holmgren","year":"2021","journal-title":"Anal. Chem."},{"key":"2026080510105737500_cit23","doi-asserted-by":"publisher","DOI":"10.1002\/rcm.9996","article-title":"Unveiling Impurity Profiling of Synthetic\nPathways of Organophosphorus Chlorpyrifos Through LC-HRMS Metabolomics-Based\nApproaches","author":"Orlandi","year":"2025","journal-title":"Rapid Commun. Mass Spectrom."},{"key":"2026080510105737500_cit24","doi-asserted-by":"publisher","first-page":"100379","DOI":"10.1016\/j.forc.2021.100379","article-title":"Machine\nLearning Model for Detecting\nFentanyl Analogs from Mass Spectra","volume":"27","author":"Koshute","year":"2022","journal-title":"Forensic\nChem."},{"issue":"9","key":"2026080510105737500_cit25","doi-asserted-by":"publisher","first-page":"1493","DOI":"10.1093\/bioinformatics\/btu813","article-title":"Workflow4Metabolomics:\nA Collaborative Research Infrastructure for Computational Metabolomics","volume":"31","author":"Giacomoni","year":"2015","journal-title":"Bioinformatics"},{"issue":"1","key":"2026080510105737500_cit26","doi-asserted-by":"publisher","first-page":"92","DOI":"10.2174\/2213235X11301010092","article-title":"Multivariate Analysis in Metabolomics","volume":"1","author":"Worley","year":"2012","journal-title":"Curr. Metabolomics"},{"key":"2026080510105737500_cit27","unstructured":"European Medicines Agency.\n          \n          Guideline\non Bioanalytical\nMethod Validation, European Medicines Agency, Committee for Medicinal\nProducts for Human Use, London; European\nMedicines Agency, 2011. https:\/\/www.ema.europa.eu\/en\/bioanalytical-method-validation. accessed 04 September 2019."},{"issue":"1","key":"2026080510105737500_cit28","doi-asserted-by":"publisher","first-page":"37","DOI":"10.1016\/j.chroma.2008.10.121","article-title":"Validation and Uncertainty Study\nof a Comprehensive List of 160 Pesticide Residues in Multi-Class Vegetables\nby Liquid Chromatography\u2013Tandem Mass Spectrometry","volume":"1215","author":"Kmella\u0301r","year":"2008","journal-title":"J. Chromatogr. A"},{"issue":"9","key":"2026080510105737500_cit29","doi-asserted-by":"publisher","first-page":"097008","DOI":"10.1289\/EHP4713","article-title":"Generating the Blood\nExposome Database Using a Comprehensive Text\nMining and Database Fusion Approach","volume":"127","author":"Barupal","year":"2019","journal-title":"Environ.\nHealth Perspect."},{"issue":"9","key":"2026080510105737500_cit30","doi-asserted-by":"publisher","first-page":"1255","DOI":"10.1039\/D1EM00178G","article-title":"Chlorpyrifos in Environment and Food:\nA Critical Review of Detection Methods and Degradation Pathways","volume":"23","author":"Nandhini","year":"2021","journal-title":"Environ. Sci.: Processes Impacts"},{"issue":"237","key":"2026080510105737500_cit31","doi-asserted-by":"publisher","first-page":"145","DOI":"10.1016\/j.tox.2007.05.007","article-title":"Comparative\nPharmacokinetics of the Organophosphorus Insecticide Chlorpyrifos\nand Its Major Metabolites Diethylphosphate, Diethylthiophosphate and\n3,5,6-Trichloro-2-Pyridinol in the Rat","volume":"237","author":"Timchalk","year":"2007","journal-title":"Toxicology"},{"key":"2026080510105737500_cit32","doi-asserted-by":"publisher","first-page":"118212","DOI":"10.1016\/j.envres.2024.118212","article-title":"Biodegradation of Chlorpyrifos Pollution from Contaminated Environment\n- A Review on Operating Variables and Mechanism","volume":"248","author":"Bosu","year":"2024","journal-title":"Environ. Res."},{"issue":"3","key":"2026080510105737500_cit33","doi-asserted-by":"publisher","first-page":"304","DOI":"10.1556\/1326.2021.00930","article-title":"LC-MS\/MS Monitoring\nfor Explosives Residues and OGSR with Diverse Ionization Temperatures\nin Soil & Hands: 30 minutes for Extraction + Elution","volume":"34","author":"Sener","year":"2022","journal-title":"Acta Chromatogr."},{"key":"2026080510105737500_cit34","doi-asserted-by":"publisher","first-page":"397","DOI":"10.1021\/acs.estlett.4c00032","article-title":"Tracking Aromatic\nAmines from Sources to Surface Waters","volume":"11","author":"Edebali","year":"2024","journal-title":"Environ.\nSci."},{"issue":"4","key":"2026080510105737500_cit35","doi-asserted-by":"publisher","first-page":"807","DOI":"10.1111\/j.1556-4029.2008.00752.x","article-title":"Desorption Electrospray Tandem MS (DESI-MSMS) Analysis\nof Methyl Centralite and Ethyl Centralite as Gunshot Residues on Skin\nand Other Surfaces","volume":"53","author":"Zhao","year":"2008","journal-title":"J. Forensic Sci."},{"key":"2026080510105737500_cit36","doi-asserted-by":"publisher","first-page":"110180","DOI":"10.1016\/j.forsciint.2020.110180","article-title":"Identification and Differentiation of Commercial and Military Explosives\nvia High Performance Liquid Chromatography High Resolution Mass Spectrometry\n(HPLC-HRMS), X-Ray Diffractometry (XRD) and X-Ray Fluorescence Spectroscopy\n(XRF): Towards a Forensic Substance Database on Explosives","volume":"308","author":"Schachel","year":"2020","journal-title":"Forensic Sci. Int."},{"key":"2026080510105737500_cit37","doi-asserted-by":"publisher","first-page":"100585","DOI":"10.1016\/j.forc.2024.100585","article-title":"Detection\nof Explosives Residue Using a Novel Subsampling Technique for DART-HRMS\nAnalysis","volume":"39","author":"Estevanes","year":"2024","journal-title":"Forensic Chem."},{"issue":"3","key":"2026080510105737500_cit38","doi-asserted-by":"publisher","first-page":"211","DOI":"10.1007\/s11306-007-0082-2","article-title":"Proposed Minimum Reporting Standards for Chemical Analysis:\nChemical Analysis Working Group (CAWG) Metabolomics Standards Initiative\n(MSI)","volume":"3","author":"Sumner","year":"2007","journal-title":"Metabolomics"}],"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.6c00112","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jamsef\/article-pdf\/37\/8\/1848\/65886976\/jasms.6c00112.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jamsef\/article-pdf\/37\/8\/1848\/65886976\/jasms.6c00112.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T14:16:02Z","timestamp":1785939362000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jamsef\/article\/37\/8\/1848\/5207172\/Nontargeted-LC-HRMS-Based-Strategies-as-a-Tool-to"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,13]]},"references-count":38,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2026,7,13]]},"published-print":{"date-parts":[[2026,8,5]]}},"URL":"https:\/\/doi.org\/10.1021\/jasms.6c00112","relation":{},"ISSN":["1044-0305","1879-1123"],"issn-type":[{"value":"1044-0305","type":"print"},{"value":"1879-1123","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,13]]}}}