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Hydrophilic Interaction Liquid Chromatography Tandem Mass Spectrometry Methylphosphonic Acid Determination in Water Samples after Derivatization with p-Bromophenacyl Bromide

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Abstract

Methylphosphonic acid is the most stable hydrolysis product of organophosphate nerve agents, which persist in environmental samples for a long time. A highly sensitive method of methylphosphonic acid detection in environmental waters has been developed and validated. Derivatization process and stability of p-bromophenacyl bromide methylphosphonic acid derivate were studied. Derivate was stable for 2 days and water content no greater than 7 % did not influence the reaction yield. The analyte concentration step in a rotary evaporator was employed prior to analysis. Detection of the pre-column methylphosphonic acid derivatization product was carried out using tandem mass spectrometry with electrospray ionization after hydrophilic interaction liquid chromatography separation. Evaporation recovery of 90 % was obtained. The intraday and interday repeatability were 6 and 25 %, respectively. Matrix effect influence was not observed. The hydrophilic interaction chromatography method results in excellent peak shape at adequate retention time. Developed approach successfully combines relatively fast derivatization and sample preparation with hydrophilic interaction chromatography and tandem mass spectrometry which allows to achieve the lowest limit of detection (0.1 ng mL−1) for methylphosphonic acid in spiked environmental waters in comparison with other HPLC techniques.

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References

  1. Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and their Destruction (1997). Technical Secretariat of the Organization for the Prohibition of Chemical Weapons, The Hague

  2. Pardasani D, Palit M, Gupta AK, Kanaujia PK, Sekhar K, Dubey DK (2006) Microemulsion mediated in situ derivatization–extraction and gas chromatography–mass spectrometric analysis of alkylphosphonic acids. J Chromatogr A 1108:166–175

    Article  CAS  Google Scholar 

  3. Kataoka M, Tsunoda N, Ohta H, Tsuge K, Takesako H, Seto Y (1998) Effect of cation-exchange pretreatment of aqueous soil extracts on the gas chromatographic–mass spectrometric determination of nerve agent hydrolysis products after tert.-butyldimethylsilylation. J Chromatogr A 824:211–221

    Article  CAS  Google Scholar 

  4. Kataoka M, Tsuge K, Seto Y (2000) Efficiency of pretreatment of aqueous samples using a macroporous strong anion-exchange resin on the determination of nerve gas hydrolysis products by gas chromatography–mass spectrometry after tert-butyldimethylsilylation. J Chromatogr A 891:295–304

    Article  CAS  Google Scholar 

  5. Sng MT, Ng WF (1999) In-situ derivatization of degradation products of chemical warfare agents in water by solid-phase microextraction and gas chromatographic–mass spectrometric analysis. J Chromatogr A 832:173–182

    Article  CAS  Google Scholar 

  6. Sega GA, Tomkins BA, Griest WH (1997) Analysis of methylphosphonic acid, ethyl methylphosphonic acid and isopropyl methylphosphonic acid at low microgram per liter levels in groundwater. J Chromatogr A 790:143–152

    Article  CAS  Google Scholar 

  7. Richardson DD, Caruso JA (2007) Derivatization of organophosphorus nerve agent degradation products for gas chromatography with ICPMS and TOF-MS detection. Anal Bioanal Chem 388:809–823

    Article  CAS  Google Scholar 

  8. Black RM, Read RW (1997) Application of liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry, and tandem mass spectrometry, to the analysis and identification of degradation products of chemical warfare agents. J Chromatogr A 759:79–92

    Article  CAS  Google Scholar 

  9. Hayes TL, Kenny DV, Hernon-Kenny L (2004) Feasibility of direct analysis of saliva and urine for phosphonic acids and thiodiglycol-related species associated with exposure to chemical warfare agents using LC-MS/MS. J Med Chem Def 2:121–144

    Google Scholar 

  10. Kubachka KM, Richardson DD, Heitkemper DT, Caruso JA (2008) Detection of chemical warfare agent degradation products in foods using liquid chromatography coupled to inductively coupled plasma mass spectrometry and electrospray ionization mass spectrometry. J Chromatogr A 1202:124–131

    Article  CAS  Google Scholar 

  11. Kingery AF, Allen HE (1994) Ion chromatographic separation of closely related nerve agent degradation products using an organic modifier to provide selectivity. Anal Chem 66:155–159

    Article  CAS  Google Scholar 

  12. Mawhinney DB, Hamelin EI, Fraser R, Silva SS, Pavlopoulos AJ, Kobelski RJ (2007) The determination of organophosphonate nerve agent metabolites in human urine by hydrophilic interaction liquid chromatography tandem mass spectrometry. J Chromatogr B 852:235–243

    Article  CAS  Google Scholar 

  13. Røen BT, Sellevag SR, Lundanes E (2013) On-line solid phase extraction-liquid chromatography–mass spectrometry for trace determination of nerve agent degradation products in water samples. ACA 761:109–116

    Google Scholar 

  14. Katagi M, Tatsuno M, Nishikawa M, Tsuchihashi H (1999) On-line solid-phase extraction liquid chromatography-continuous flow frit fast atom bombardment mass spectrometric and tandem mass spectrometric determination of hydrolysis products of nerve agents alkyl methylphosphonic acids by p-bromophenacyl derivatization. J Chromatogr A 833:169–179

    Article  CAS  Google Scholar 

  15. Matuszewsky BK, Constanzer ML, Chavez-Eng CM (2003) Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC–MS/MS. Anal Chem 75:3019–3030

    Article  Google Scholar 

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Authors and Affiliations

  1. Chemistry Department, Lomonosov Moscow State University, 119991, Moscow, Russia

    Igor Rodin, Timur Baygildiev, Andrey Stavrianidi, Arcady Braun & Oleg Shpigun

  2. Laboratory for the Chemical and Analytical Control of Military Research Centre, Brigadirsky Pereulok, 13, 105005, Moscow, Russia

    Igor Rybalchenko

Authors
  1. Igor Rodin
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  2. Timur Baygildiev
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  3. Andrey Stavrianidi
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  4. Arcady Braun
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  5. Igor Rybalchenko
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  6. Oleg Shpigun
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Correspondence to Igor Rodin.

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Rodin, I., Baygildiev, T., Stavrianidi, A. et al. Hydrophilic Interaction Liquid Chromatography Tandem Mass Spectrometry Methylphosphonic Acid Determination in Water Samples after Derivatization with p-Bromophenacyl Bromide. Chromatographia 78, 585–591 (2015). https://doi.org/10.1007/s10337-015-2862-6

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  • DOI: https://doi.org/10.1007/s10337-015-2862-6

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