Sample Preparation for Analysis of Chemicals Related to the Chemical Weapons Convention in an Off‐site Laboratory

Kuitunen, Marja‐Leena

doi:10.1002/9780470027318.a0410.pub2

Cited by 4 publications

(8 citation statements)

References 86 publications

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“…The use of CWAs can be verified by the identification of convention related compounds (CRCs) in environmental and synthetic matrices. 15,16 In this context, off-site analysis related to CRCs plays an essential role to validate the offense of CWC. During on-site inspections, OPCW inspectors collect samples from the production, storage, and suspected sites of chemical weapon activity.…”

Section: Introductionmentioning

confidence: 99%

“…During on-site inspections, OPCW inspectors collect samples from the production, storage, and suspected sites of chemical weapon activity. 15,16 For the unambiguous identification, these complex samples are sent to the "designated laboratories" for offsite analysis. 15−17 Among these collected samples, organic liquids are very common as these can be used as a medium for spread of CWAs or be used as a solvent during synthesis and storage.…”

Section: Introductionmentioning

confidence: 99%

“…23−25 However, most of the sources of organic samples are usually adulterated with hydrocarbon backgrounds or other interfering chemicals, which create difficulties in chromatographic and spectroscopic analysis. 15,16,19,20 In the presence of hydrocarbon backgrounds or interfering chemicals, both GC−MS and NMR analyses may give spurious information because analyte signals may eclipsed under background signals. 26−30 Therefore, sample preparation is of utmost value for cleanup of the interfering backgrounds and successful identification of the desired analytes.…”

Section: Introductionmentioning

confidence: 99%

“…The use of CWAs can be verified by the identification of convention related compounds (CRCs) in environmental and synthetic matrices. , In this context, off-site analysis related to CRCs plays an essential role to validate the offense of CWC. During on-site inspections, OPCW inspectors collect samples from the production, storage, and suspected sites of chemical weapon activity. , For the unambiguous identification, these complex samples are sent to the “designated laboratories” for off-site analysis. − Among these collected samples, organic liquids are very common as these can be used as a medium for spread of CWAs or be used as a solvent during synthesis and storage. The analysis of organic samples from different sources like organic waste, incineration waste, engine or machine fuel, silicon oil, or vacuum pump oil provides the information regarding the suspected area or production plant prohibited by CWC.…”

Section: Introductionmentioning

confidence: 99%

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Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and ¹H NMR Analysis of Chemical Weapons Convention Related Compounds

Roy

Mazumder

et al. 2019

ACS Appl. Mater. Interfaces

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The strict monitoring and precise measurements of chemical warfare agents (CWAs) in environmental and other complex samples with high accuracy have great practical significance from the forensic and Chemical Weapons Convention (CWC) verification point of view. Therefore, this study was aimed to develop an efficient extraction and enrichment method for identification and quantification of toxic agents, especially with high sensitivity and multidetection ability in complex samples. It is the first study on solid-phase extraction (SPE) of CWAs and their related compounds from hydrocarbon backgrounds using covalent triazine-based frameworks (CTFs). This nitrogenrich CTF sorbent has shown an excellent SPE performance toward sample cleanup by selective elimination of hydrocarbon backgrounds and enrich the CWC related analytes in comparison with the conventional and other reported methods. The best enrichment of the analytes was found with the washing solvent (1 mL of n-hexane) and the extraction solvent (1 mL of dichloromethane). Under the optimized conditions, the SPE method had good linearity in the concentration range of 0.050−10.0 μg mL −1 for organophosphorus esters, 0.040− 20.0 μg mL −1 for nerve agents, and 0.200−20.0 μg mL −1 for mustards with correlation coefficients (r 2 ) between 0.9867 and 0.9998 for all analytes. Limits of detection (S/N = 3:1) in the SIM mode were found to be in the range of 0.015−0.050 μg mL −1 for organophosphorus esters, 0.010−0.030 μg mL −1 for nerve agents, and 0.050−0.100 μg mL −1 for blister agents. Limits of quantification (S/N = 10:1) were found in the range of 0.050−0.200 μg mL −1 for organophosphorus esters, 0.040−0.100 μg mL −1 for nerve agents, and 0.180−0.350 μg mL −1 for blister agents in the SIM mode. The recoveries of all analytes ranged from 87 to 100% with the relative standard deviations ranging from 1 to 8%. This method was also successfully applied for the sample preparation of 1 H NMR analysis of sulfur and nitrogen mustards in the presence of hydrocarbon backgrounds. Therefore, this SPE method provides the single sample preparation for both NMR and GC−MS analyses. KEYWORDS: triazine-based covalent organic framework, solid-phase extraction, chemical warfare agents, hydrocarbon backgrounds, organic samples, GC−MS and 1 H NMR analysis

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and ¹H NMR Analysis of Chemical Weapons Convention Related Compounds

Roy

Mazumder

et al. 2019

ACS Appl. Mater. Interfaces

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“…[8][9][10][11] Most of the environmental samples consist of different background chemicals or matrix-associated chemicals that are expected to mask the CWAs and their reaction/degradation products, especially when present at low ppm concentrations. 12,13 In such cases, application of suitable methods of sample extraction, cleanup, and detection technique is crucial, and many reports are available in literature in these lines. Among the detection techniques, gas chromatography (GC) coupled with element-specific detectors with mass spectrometry (MS) detector [14][15][16][17][18] have been the routine choice for the screening of CWC-related chemicals and their degradation/reaction products.…”

Section: Introductionmentioning

confidence: 99%

Gas chromatography/mass spectrometry analysis of reaction products of sulfur mustards with phenol

Veeresham

Sandeep

Reddy

et al. 2019

Eur J Mass Spectrom (Chichester)

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Screening of chemicals related to chemical weapons convention including their all possible degradation and reaction products in environmental samples is important in the organization for prohibition of chemical weapons verification process. Sulfur mustards, commonly known as blistering agents, are included in schedule 1 chemicals of chemical weapons convention. Because of the presence of chlorine atoms in sulfur mustards, they are highly reactive and prone to react with other organic molecules such as phenols to produce corresponding reaction products. Thus, it is important to screen for not only the sulfur mustards but also their reaction products for verification process. The sulfur mustards and their degradation products have been routinely analyzed by gas chromatography/mass spectrometry method, however, the methods are yet to establish for the reaction products. In this study, the reaction products of the sulfur mustards with phenol (compounds 1–7) were studied by gas chromatography/mass spectrometry under electron ionization and chemical ionization conditions. The EI spectra of 1–7 displayed molecular ion and characteristic fragments that provided structure information. Mostly the fragment ions were due to homolytic cleavages involving C–O, C–S, and C–C cleavages. The methane or isobutane CI spectra showed M+., [M + H]+, and [M − H]+ ions including reagent specific adduct ions. The CI spectra also showed other adduct ions formed by association of analyte molecule with its most abundant fragment ion. The gas chromatography/retention index values were also calculated, which support unambiguous identification of targeted molecules in suspected environmental samples. The method was demonstrated for detection of the targeted molecules spiked in soil samples.

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Identification of acidic degradation products of chemical warfare agents by methylation with trimethylsilyldiazomethane and gas chromatography–mass spectrometry

et al. 2022

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Sensitive and reliable analysis of alkylphosphonic acids (APAs) and 2-(N,N-dialkylamino)ethanesulfonic acids (SAs), the degradation products of chemical warfare agents (CWAs), is one of the most important tasks for verification of the Chemical Weapons Convention (CWC). Unambiguous identification of these chemicals is required in a variety of environmental matrices, including soil and water. These acids with low volatility are very polar, and efficient and reliable methylation methods for their derivatization are needed for analysis with gas chromatography–mass spectrometry (GC–MS). In this study, the derivatization conditions for trimethylsilyldiazomethane (TMSDAM) methylation were optimized for rapid GC–MS screening. Optimized methylation of APAs and SAs with TMSDAM was compared with methylation with diazomethane. The TMSDAM methylation of SAs and benzilic acid was further compared with silylation with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide. The significance and necessity of cation exchange prior to derivatization and analysis were tested on samples with a high inorganic background. A recommendation to use the method for methylation of water samples and aqueous extracts using TMSDAM is given. The robustness of the method was illustrated by the successful identification of APAs and SAs in aqueous samples from proficiency tests organized by the Organisation for the Prohibition of Chemical Weapons.

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Sample Preparation for Analysis of Chemicals Related to the Chemical Weapons Convention in an Off‐site Laboratory

Cited by 4 publications

References 86 publications

Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and ¹H NMR Analysis of Chemical Weapons Convention Related Compounds

Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and ¹H NMR Analysis of Chemical Weapons Convention Related Compounds

Gas chromatography/mass spectrometry analysis of reaction products of sulfur mustards with phenol

Identification of acidic degradation products of chemical warfare agents by methylation with trimethylsilyldiazomethane and gas chromatography–mass spectrometry

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Sample Preparation for Analysis of Chemicals Related to the Chemical Weapons Convention in an Off‐site Laboratory

Cited by 4 publications

References 86 publications

Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and 1H NMR Analysis of Chemical Weapons Convention Related Compounds

Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and 1H NMR Analysis of Chemical Weapons Convention Related Compounds

Gas chromatography/mass spectrometry analysis of reaction products of sulfur mustards with phenol

Identification of acidic degradation products of chemical warfare agents by methylation with trimethylsilyldiazomethane and gas chromatography–mass spectrometry

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Product

Resources

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Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and ¹H NMR Analysis of Chemical Weapons Convention Related Compounds

Triazine-Based Covalent Organic Framework: A Promising Sorbent for Efficient Elimination of the Hydrocarbon Backgrounds of Organic Sample for GC–MS and ¹H NMR Analysis of Chemical Weapons Convention Related Compounds