Effect of cation-exchange pretreatment of aqueous soil extracts on the gas chromatographic–mass spectrometric determination of nerve agent hydrolysis products after tert.-butyldimethylsilylation

Kataoka, Mieko; Tsunoda, Noriko; Ohta, Hikoto; Tsuge, Kouichiro; Takesako, Hiroshi; Seto, Yasuo

doi:10.1016/s0021-9673(98)00674-8

Cited by 53 publications

(33 citation statements)

References 15 publications

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“…The studies have suggested that MPA, a divalent ion, is derivatized more efficiently in acidic solution than in basic solution (2), suggesting that metal ions in basic solution could form salts with the anion, which could hinder derivatization (1). This effect was also noted previously for IMPA and EMPA, which are monovalent anions (17). The observation is consistent with the difference in the decontamination solutions used for the two agents.…”

Section: Resultssupporting

confidence: 90%

Analysis of Chemical Weapons Decontamination Waste from Old Ton Containers from Johnston Atoll Using Multiple Analytical Methods

Creasy¹,

Brickhouse²,

Morrissey³

et al. 1999

Environ. Sci. Technol.

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Decontamination waste from chemical weapons (CW) agents has been stored in ton containers on Johnston Atoll since 1971. The waste was recently sampled and analyzed to determine its chemical composition in preparation for disposal. Due to the range of products and analytical requirements, multiple chromatographic and spectroscopic methods were necessary, including gas chromatography/ mass spectrometry (GC/MS), gas chromatography/ atomic emission detection (GC/AED), liquid chromatography/ mass spectrometry (LC/MS), capillary electrophoresis (CE), and nuclear magnetic resonance spectroscopy (NMR). The samples were screened for residual agents. No residual sarin (GB) or VX was found to detection limits of 20 ng/mL, but 3% of the samples contained residual sulfur mustard (HD) at <140 ng/mL. Decontamination products of agents were identified. The majority (74%) of the ton containers were documented correctly, in that the observed decontamination products were in agreement with the labeled agent type, but for a number of the containers, the contents were not in agreement with the labels. In addition, arsenic compounds that are decontamination products of the agent lewisite (L) were observed in a few ton containers, suggesting that lewisite was originally present but not documented. This study was a prototype to demonstrate the level of effort required to characterize old bulk CW-related waste.

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Section: Resultssupporting

confidence: 90%

Analysis of Chemical Weapons Decontamination Waste from Old Ton Containers from Johnston Atoll Using Multiple Analytical Methods

Creasy¹,

Brickhouse²,

Morrissey³

et al. 1999

Environ. Sci. Technol.

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“…Detection limits for RMPAs and MPA derivatives were 100 ng/ml in the reaction vial (S/N = 3) for extracted ion chromatograms. 28) …”

Section: Nerve Gas Hydrolysis Products For Gc-msmentioning

confidence: 99%

“…Moreover, some neutral compounds, such as carbohydrates, which contain hydroxide groups competed against the phosphonates in the silylation reaction and suppressed the TBDMS derivatization. 28,31) Several investigations on cleanup of nerve gas hydrolysis products using solid phase extraction (SPE) have been reported, 23,25,[32][33][34] and some drawbacks were found such as low recoveries of RMPAs and MPA and insufficient information about SPE procedures. We attempted some types of SPE including strong cation-exchanger, 28) anionexchanger and reversed-phase 31,35) followed by TBDMS derivatization.…”

Section: Fig 4 Effects Of Alkaline Earth Metals On the Detection Yimentioning

confidence: 99%

Laboratory Identification of the Nerve Gas Hydrolysis Products Alkyl Methylphosphonic Acids and Methylphosphonic Acid, by Gas Chromatography-mass Spectrometry after <i>tert</i>-Butyldimethylsilylation

Kanamori-Kataoka

Seto

2008

JOURNAL OF HEALTH SCIENCE

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Alkyl methylphosphonic acids (RMPAs) and methylphosphonic acid (MPA), both nerve gas hydrolysis products, can be identified by gas chromatography-mass spectrometry (GC-MS). We adopted tertbutyldimethylsilylation (TBDMS) as a derivatization technique for the identification of these products by GC-MS. We found that it was difficult to detect RMPAs and MPA from evidence specimens such as soils and body fluids, and ascertained several causes for this. The first is the interference from the TBDMS derivatization. It was determined that the TBDMS derivatization of RMPAs and MPA was suppressed in the presence of divalent metal cations such as calcium and magnesium ions, as well as some neutral compounds like carbohydrates. A cleanup procedure using a strong anion-exchanger (SAX)-solid phase extraction (SPE) method was optimized to remove the interfering compounds. The second reason that detection was difficult was because of strong matrix adsorption. We elucidated that the aqueous extraction recoveries for all phosphonates were inversely correlated with the phosphate adsorption coefficient in the soil samples. To diminish the adsorption of phosphonates to soils, a method of alkali extraction was adopted. For human serum samples, we adopted acetonitrile or trichloroacetic acid deproteinization which worked to break the binding between the proteins and the phosphonates. The detection yields of RMPAs and MPA from soils and human serum were dramatically increased using these pretreatment procedures combined with extraction and/or SAX-SPE. The method of SAX-SPE was applied to various types of samples, such as seawater, drinks and human urine, and good detection yields of RMPAs and MPA were provided by GC-MS.

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“…Methylphosphonic acid monoisopropyl ester (IMPA) was prepared as we previously reported (10). To a stirred solution of 309 mg of dicyclohexylcarbodiimide (DCC) in 2 ml of dry dichloromethane (CH 2 Cl 2 ), a solution of 200 mg (1.45 mmol) of IMPA in 2 ml of CH 2 Cl 2 was added at room temperature (RT).…”

Section: Preparation Of Inmpmentioning

confidence: 99%

New Safe Method for Preparation of Sarin-Exposed Human Erythrocytes Acetylcholinesterase Using Non-Toxic and Stable Sarin Analogue Isopropyl p-Nitrophenyl Methylphosphonate and its Application to Evaluation of Nerve Agent Antidotes

et al. 2006

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Effect of cation-exchange pretreatment of aqueous soil extracts on the gas chromatographic–mass spectrometric determination of nerve agent hydrolysis products after tert.-butyldimethylsilylation

Cited by 53 publications

References 15 publications

Analysis of Chemical Weapons Decontamination Waste from Old Ton Containers from Johnston Atoll Using Multiple Analytical Methods

Analysis of Chemical Weapons Decontamination Waste from Old Ton Containers from Johnston Atoll Using Multiple Analytical Methods

Laboratory Identification of the Nerve Gas Hydrolysis Products Alkyl Methylphosphonic Acids and Methylphosphonic Acid, by Gas Chromatography-mass Spectrometry after <i>tert</i>-Butyldimethylsilylation

New Safe Method for Preparation of Sarin-Exposed Human Erythrocytes Acetylcholinesterase Using Non-Toxic and Stable Sarin Analogue Isopropyl p-Nitrophenyl Methylphosphonate and its Application to Evaluation of Nerve Agent Antidotes

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