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Combination of solid phase extraction and in vial solid phase derivatization using a strong anion exchange disk for the determination of nerve agent markers
Umeå University, Faculty of Science and Technology, Department of Chemistry. (Swedish Defence Research Agency, FOI CBRN Defence and Security, Umeå, Sweden)
Swedish Defence Research Agency, FOI CBRN Defence and Security, Umeå, Sweden.
Swedish Defence Research Agency, FOI CBRN Defence and Security, Umeå, Sweden.
Swedish Defence Research Agency, FOI CBRN Defence and Security, Umeå, Sweden. (Swedish Armed Forces, National CBRN-Defence Centre, Umeå, Sweden)
2009 (English)In: Journal of Chromatography A, Vol. 1216, no 48, 8452-9 p.Article in journal (Refereed) Published
Abstract [en]

Alkylphosphonic acids (APAs) are degradation products and chemical markers of organophosphorous (OP) nerve agents (chemical warfare agents). Anion exchange disk-based solid phase extraction (SPE) has been combined with in vial solid phase derivatization (SPD) and GC-MS analysis for the determination of APAs in aqueous samples. The optimization of critical method parameters, such as the SPD reaction, was achieved using statistical experimental design and multivariate data analysis. The optimized method achieved quantitative recoveries in the range from 83% to 101% (n=13, RSD from 4% to 10%). The method was sensitive, with LODs in SIM mode of 0.14ppb, and demonstrated excellent linearity with an average R(2)>/=0.99 over the concentration range of 0.07-1.4ppm in full scan mode and from 0.14ppb to 14ppb in SIM mode. For forensic applications, aqueous samples containing APAs at concentrations exceeding 14ppb were concentrated and target analytes were successfully identified by spectral library and retention index matching. Method robustness was evaluated using aqueous samples from the official OPCW Proficiency Test (round 19) and all APAs present in the sample were conclusively identified. The SPE disk retained the underivatized APAs in a stable condition for extended periods of time. No significant losses of APAs from the disk were observed over a 36-day period. Overall, the method is well suited to the qualitative and quantitative analysis of degradation markers of OP nerve agents in aqueous matrices with simplicity, a low risk of cross-contamination and trace level sensitivity.

Place, publisher, year, edition, pages
Elsevier , 2009. Vol. 1216, no 48, 8452-9 p.
Keyword [en]
Chemical warfare agents, Alkylphosphonic acids, Disk solid phase extraction, Solid phase derivatization, Anion exchange disk, Statistical experimental design
National Category
Chemical Sciences
URN: urn:nbn:se:umu:diva-26845DOI: 10.1016/j.chroma.2009.10.017OAI: diva2:274360
Available from: 2009-10-28 Created: 2009-10-28 Last updated: 2012-05-04Bibliographically approved
In thesis
1. Simplified Routines for Sample Preparation and Analysis of Chemical Warfare Agent Degradation Products
Open this publication in new window or tab >>Simplified Routines for Sample Preparation and Analysis of Chemical Warfare Agent Degradation Products
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The thesis describes the development of new and improved methods for analyzing degradation markers from organophosphorus Chemical Warfare Agents (CWAs).

Paper I and II describes an innovative and significantly improved method for the enrichment, derivatization (trimethysilylation) and GC-MS analysis of a broad range of organophosphorus CWAs degradation markers, namely the alkylphosphonic acids and a zwitterionic compound. That was achieved using solid phase disc extraction in combination with solid phase derivatization. The new method overcomes most limitations observed with existing techniques: it offers almost 100 % recoveries, requires no elution or evaporation steps, facilitates miniaturization of the solid sorbent and reagent, is compatible with in-vial derivatization, and minimizes the chromatographic background due to the use of a highly selective anion exchange sorbent disc.

Paper III describes the development of new fluorinated diazomethane derivatization reagents and their evaluation for rapid and high sensitivity screening and identification of nerve agent degradation markers. The reagents are water-tolerant to some extent, which simplifies the derivatization step. The best reagent identified was 3,5-bis(trifluoromethyl)benzyl diazomethane, which outperformed the other reagent isomers tested and also the established commercial alternative, pentafluorobenzylbromide, allowing for the rapid (5 min) and direct derivatization of a 25 μL aqueous sample in acetonitrile. The spectra of the formed derivatives (high-energy collision induced fragmentation MS/MS) were used to construct a database (Paper IV) that proved to be superior in terms of match factor and probability compared to EI data gathered for trimethylsilyl derivatives. The study also focused on efforts towards achieving detailed structure information on the alkyl chains of the compounds in question using diagnostic ion interpretation.

The final paper (paper V) describes the first rapid direct derivatization method for analyzing nerve agent metabolites in urine at trace levels. The method is based on the derivative from the paper III and the unambiguous identification was proven using a combination of low resolution and high resolution negative ion chemical ionization selected ion monitoring techniques.

Novel results presented in these papers include: the first in-situ derivatization of alkylphosphonic acids on an SPE disc; the first direct derivatization of nerve agent markers in water and biomedical samples; the first high sensitivity GC-MS screening for these markers; and the first highly reproducible high-energy isomer specific CID MS/MS library. Overall, the results presented in this thesis represent significant contributions to the analysis of nerve agent degradation products.

Place, publisher, year, edition, pages
Umeå: Umeå University, 2012. 58 p.
Nerve agents, Alkyl alkylphosphonic acids, Solid phase derivatization, Fluorinated diazomethane reagent, High-energy collision induced dissociation, CID MS/MS library
National Category
Chemical Sciences
Research subject
Analytical Chemistry
urn:nbn:se:umu:diva-54639 (URN)978-91-7459-440-9 (ISBN)
Public defence
2012-05-25, KB3B1, KBC-huset, Umeå University, Umeå, 09:00 (English)
Available from: 2012-05-04 Created: 2012-05-03 Last updated: 2012-05-04Bibliographically approved

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