Efficient derivatization of methylphosphonic and aminoethylsulfonic acids related to nerve agents simultaneously in soils using trimethyloxonium tetrafluoroborate for their enhanced, qualitative detection and identification by EI-GC–MS and GC–FPD
Abstract
Trimethyloxonium tetrafluoroborate (TMO·BF4) has been used here in the simultaneous derivatization of phosphonic and 2-aminoethylsulfonic acids related to nerve agents in different soils for their enhanced detection and identification by electron ionization gas chromatography-mass spectrometry (EI-GC–MS). The panel of acids consisted of five Schedule 2 phosphonic acids (methyl methylphosphonic acid, ethyl methylphosphonic acid, isopropyl methylphosphonic acid, pinacolyl methylphosphonic acid and cyclohexyl methylphosphonic acid) along with two sulfonic acids, N,N-diethyl-2-aminoethylsulfonic acid and N,N-diisopropyl-2-aminoethylsulfonic acid. The acids were converted to their corresponding methyl esters at ambient temperature when present at a 10 μg g-1 concentration in three separate soils: Virginia type A soil, Ottawa sand and Nebraska EPA soil. The concentration of the acids reflects values typically encountered during proficiency tests (PTs) administered annually by the Organisation for the Prohibition of Chemical Weapons (OPCW). Derivatization times to yield detectable signals for the methyl ester products for all the acids was found to vary among all three soil samples, however, it was found that generally the most optimal time across all the matrices involved was 3 h after the addition of TMO·BF4. Concomitantly, the analysis of the samples was complemented using GC coupled to flame photometric detection (GC–FPD). The inclusion of GC–FPD inmore »
- Authors:
-
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate. Nuclear and Chemical Sciences Division. Forensic Science Center
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Forensic Science Center; United States Air Force Academy, USAF Academy, CO (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1512628
- Report Number(s):
- LLNL-JRNL-738410
Journal ID: ISSN 0379-0738; 889829
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Forensic Science International
- Additional Journal Information:
- Journal Volume: 288; Journal ID: ISSN 0379-0738
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nerve agents; phosphonic acids; aminoethylsulfonic acids; methylation; GC–MS; OPCW
Citation Formats
Valdez, Carlos A., Marchioretto, Mira K., Leif, Roald N., and Hok, Saphon. Efficient derivatization of methylphosphonic and aminoethylsulfonic acids related to nerve agents simultaneously in soils using trimethyloxonium tetrafluoroborate for their enhanced, qualitative detection and identification by EI-GC–MS and GC–FPD. United States: N. p., 2018.
Web. doi:10.1016/j.forsciint.2018.04.041.
Valdez, Carlos A., Marchioretto, Mira K., Leif, Roald N., & Hok, Saphon. Efficient derivatization of methylphosphonic and aminoethylsulfonic acids related to nerve agents simultaneously in soils using trimethyloxonium tetrafluoroborate for their enhanced, qualitative detection and identification by EI-GC–MS and GC–FPD. United States. https://doi.org/10.1016/j.forsciint.2018.04.041
Valdez, Carlos A., Marchioretto, Mira K., Leif, Roald N., and Hok, Saphon. Fri .
"Efficient derivatization of methylphosphonic and aminoethylsulfonic acids related to nerve agents simultaneously in soils using trimethyloxonium tetrafluoroborate for their enhanced, qualitative detection and identification by EI-GC–MS and GC–FPD". United States. https://doi.org/10.1016/j.forsciint.2018.04.041. https://www.osti.gov/servlets/purl/1512628.
@article{osti_1512628,
title = {Efficient derivatization of methylphosphonic and aminoethylsulfonic acids related to nerve agents simultaneously in soils using trimethyloxonium tetrafluoroborate for their enhanced, qualitative detection and identification by EI-GC–MS and GC–FPD},
author = {Valdez, Carlos A. and Marchioretto, Mira K. and Leif, Roald N. and Hok, Saphon},
abstractNote = {Trimethyloxonium tetrafluoroborate (TMO·BF4) has been used here in the simultaneous derivatization of phosphonic and 2-aminoethylsulfonic acids related to nerve agents in different soils for their enhanced detection and identification by electron ionization gas chromatography-mass spectrometry (EI-GC–MS). The panel of acids consisted of five Schedule 2 phosphonic acids (methyl methylphosphonic acid, ethyl methylphosphonic acid, isopropyl methylphosphonic acid, pinacolyl methylphosphonic acid and cyclohexyl methylphosphonic acid) along with two sulfonic acids, N,N-diethyl-2-aminoethylsulfonic acid and N,N-diisopropyl-2-aminoethylsulfonic acid. The acids were converted to their corresponding methyl esters at ambient temperature when present at a 10 μg g-1 concentration in three separate soils: Virginia type A soil, Ottawa sand and Nebraska EPA soil. The concentration of the acids reflects values typically encountered during proficiency tests (PTs) administered annually by the Organisation for the Prohibition of Chemical Weapons (OPCW). Derivatization times to yield detectable signals for the methyl ester products for all the acids was found to vary among all three soil samples, however, it was found that generally the most optimal time across all the matrices involved was 3 h after the addition of TMO·BF4. Concomitantly, the analysis of the samples was complemented using GC coupled to flame photometric detection (GC–FPD). The inclusion of GC–FPD in the analysis yielded stronger signals for all seven methylated analytes making their detection after merely 3 h possible relative to the ones initially obtained with EI-GC–MS. Regarding the three soils employed in our study, a greater methylating efficiency was found in the Virginia type A soil and Ottawa sand yielding results that were significantly larger in magnitude to those found during the same time points for the Nebraska EPA soil sample. Prolonged reaction times (up to 72 h) were explored to find the time for the highest yield of methyl ester production were found instead to be deleterious to the process showcasing the importance of the fast yielding nature of the process specifically in situations where time-sensitive analysis is crucial (e.g. OPCW-PT).},
doi = {10.1016/j.forsciint.2018.04.041},
journal = {Forensic Science International},
number = ,
volume = 288,
place = {United States},
year = {Fri Apr 27 00:00:00 EDT 2018},
month = {Fri Apr 27 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
History of chemical and biological warfare agents
journal, October 2005
- Szinicz, L.
- Toxicology, Vol. 214, Issue 3
Chemical warfare agents
journal, September 2008
- Chauhan, S.; Chauhan, S.; D’Cruz, R.
- Environmental Toxicology and Pharmacology, Vol. 26, Issue 2
Chemical warfare agents
journal, January 2010
- Ganesan, K.; Raza, Sk; Vijayaraghavan, R.
- Journal of Pharmacy and Bioallied Sciences, Vol. 2, Issue 3
In vivo cholinesterase inhibitory specificity of organophosphorus nerve agents
journal, December 2005
- Shih, Tsung-Ming; Kan, Robert K.; McDonough, John H.
- Chemico-Biological Interactions, Vol. 157-158
Review of Oximes in the Antidotal Treatment of Poisoning by Organophosphorus Nerve Agents
journal, January 2002
- Kassa, J.
- Journal of Toxicology: Clinical Toxicology, Vol. 40, Issue 6
Limitations and challenges in treatment of acute chemical warfare agent poisoning
journal, December 2013
- Thiermann, Horst; Worek, Franz; Kehe, Kai
- Chemico-Biological Interactions, Vol. 206, Issue 3
Oximes in organophosphate poisoning: 60 years of hope and despair
journal, November 2016
- Worek, Franz; Thiermann, Horst; Wille, Timo
- Chemico-Biological Interactions, Vol. 259
The Tokyo subway sarin attack—lessons learned
journal, September 2005
- Okumura, T.; Hisaoka, T.; Yamada, A.
- Toxicology and Applied Pharmacology, Vol. 207, Issue 2
Syrian gas attack reinforces need for better anti-sarin drugs
journal, October 2013
- Dolgin, Elie
- Nature Medicine, Vol. 19, Issue 10
Derivatization of pinacolyl alcohol with phenyldimethylchlorosilane for enhanced detection by gas chromatography–mass spectrometry
journal, January 2014
- Albo, Rebecca L. F.; Valdez, Carlos A.; Leif, Roald N.
- Analytical and Bioanalytical Chemistry, Vol. 406, Issue 21
Rapid and mild silylation of β -amino alcohols at room temperature mediated by N -methylimidazole for enhanced detectability by gas chromatography/electron ionization mass spectrometry: NMI-mediated in situ silylation of β -aminoethyl alcohols
journal, September 2014
- Valdez, Carlos A.; Leif, Roald N.; Hart, Bradley R.
- Rapid Communications in Mass Spectrometry, Vol. 28, Issue 20
31 P-Edited Diffusion-Ordered 1 H NMR Spectroscopy for the Spectral Isolation and Identification of Organophosphorus Compounds Related to Chemical Weapons Agents and Their Degradation Products
journal, November 2012
- Mayer, Brian P.; Valdez, Carlos A.; Hok, Saphon
- Analytical Chemistry, Vol. 84, Issue 23
Perhydrolysis of nerve agent VX
journal, December 1993
- Yang, Yu Chu; Szafraniec, Linda L.; Beaudry, William T.
- The Journal of Organic Chemistry, Vol. 58, Issue 25
Chemical Detoxification of Nerve Agent VX
journal, February 1999
- Yang, Yu-Chu
- Accounts of Chemical Research, Vol. 32, Issue 2
Quantitation of five organophosphorus nerve agent metabolites in serum using hydrophilic interaction liquid chromatography and tandem mass spectrometry
journal, March 2014
- Hamelin, Elizabeth I.; Schulze, Nicholas D.; Shaner, Rebecca L.
- Analytical and Bioanalytical Chemistry, Vol. 406, Issue 21
LC-MS-based procedures for monitoring of toxic organophosphorus compounds and verification of pesticide and nerve agent poisoning
journal, March 2008
- John, Harald; Worek, Franz; Thiermann, Horst
- Analytical and Bioanalytical Chemistry, Vol. 391, Issue 1
Derivatization of organophosphorus nerve agent degradation products for gas chromatography with ICPMS and TOF-MS detection
journal, March 2007
- Richardson, Douglas D.; Caruso, Joseph A.
- Analytical and Bioanalytical Chemistry, Vol. 388, Issue 4
Derivatization in Mass Spectrometry—1. Silylation
journal, February 2003
- Halket, John M.; Zaikin, Vladimir G.
- European Journal of Mass Spectrometry, Vol. 9, Issue 1
FIRM FINED FOR CHEMIST’S DEATH: SAFETY: Sepracor Canada admits lack of lab ventilation in worker fatality case
journal, May 2011
- Kemsley, Jyllian
- Chemical & Engineering News Archive, Vol. 89, Issue 19
Effective methylation of phosphonic acids related to chemical warfare agents mediated by trimethyloxonium tetrafluoroborate for their qualitative detection and identification by gas chromatography-mass spectrometry
journal, August 2016
- Valdez, Carlos A.; Leif, Roald N.; Alcaraz, Armando
- Analytica Chimica Acta, Vol. 933
Über Tertiäre Oxoniumsalze, I
journal, January 1937
- Meerwein, Hans; Hinz, Gerhard; Hofmann, Paul
- Journal für Praktische Chemie, Vol. 147, Issue 10-12
Urinary organic acid screening by solid-phase microextraction of the methyl esters
journal, August 1998
- Liebich, H. M.; Gesele, E.; Wöll, J.
- Journal of Chromatography B: Biomedical Sciences and Applications, Vol. 713, Issue 2
Analysis of sulfonic acids by gas chromatography—mass spectrometry of trimethylsilyl derivatives
journal, July 1978
- Stokke, Oddvar; Helland, Per
- Journal of Chromatography B: Biomedical Sciences and Applications, Vol. 146, Issue 1
Development of a New Method for the Identification of Degradation Products of V-Type Nerve Agents by Liquid Chromatography–Tandem Mass Spectrometry
journal, January 2014
- Lee, Jin Young; Lee, Yong Han
- Journal of Chromatographic Science, Vol. 52, Issue 10
Degradation of S -2-Di-isopropylaminoethyl O -ethyl methylphosphonothioate in soil: Phosphorus-containing products
journal, August 1976
- Verweij, Albert; Boter, Henk L.
- Pesticide Science, Vol. 7, Issue 4
Degradation of S -2-di-isopropylaminoethyl O -ethyl methylphosphonothioate in soil. Sulphur-containing products
journal, October 1977
- Kaaijk, Joke; Frijlink, Carel
- Pesticide Science, Vol. 8, Issue 5
Extraction of Nerve Agent VX from Soils
journal, May 2004
- Montauban, Cécile; Bégos, Arlette; Bellier, Bruno
- Analytical Chemistry, Vol. 76, Issue 10
Works referencing / citing this record:
Soil and Human Health: Current Status and Future Needs
journal, January 2020
- Brevik, Eric C.; Slaughter, Lindsey; Singh, Bal Ram
- Air, Soil and Water Research, Vol. 13
Figures / Tables found in this record: