Efficient Extraction of Sulfur and Nitrogen Mustards from Nonpolar Matrix and an Investigation on Their Sorption Behavior on Silica

Abstract

Extraction of vesicant class of chemical warfare agents (CWAs) such as sulfur mustard and nitrogen mustards from the environmental matrices is of prime importance, from a forensic and verification viewpoint of the Chemical Weapons Convention (CWC). For extraction of Convention Related Compounds from nonpolar organic medium, commercially available silica cartridges are used extensively, but silica cartridges exhibit limited efficiency toward vesicant classes of compounds. It is expected that sulfur mustard being nonpolar does not retain sufficiently on silica surface, and nitrogen mustards (being basic) are strongly adsorbed on acidic silica surface, resulting in their poor recoveries. Contrary to the expected higher recovery of sulfur mustard over nitrogen mustards, it was observed that the recovery of sulfur mustard was lower than that of nitrogen mustards with the silica based sorbent. The reason for this typical behavior of these agents on silica was investigated. This study was aimed to develop an analytical method for efficient extraction and enrichment of sulfur and nitrogen mustards from hydrophobic matrices. In this work, the polymeric sorbent was synthesized with polar methacrylic acid (MAA) as monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker and used for solid phase extraction (SPE) of sulfur mustard and nitrogen mustards. The extraction efficiency of the polymeric sorbent was optimized and compared with that of silica cartridges. Both classes of analytes were recovered in good amounts from the polymeric sorbent compared to silica. The extraction parameters were optimized for the proposed method which included extraction solvent ethyl acetate and washing solvent n-hexane (1 mL). The recoveries of the analytes ranged from 75 to 87% with relative standard deviations (RSDs) lower than 9%. The limit of detection (LOD) was found to be in the range of 0.075-0.150 μg mL, and limit of quantification (LOQ) was >0.25 μg mL. The linear dynamic range of optimized method was found to be 0.50-20 μg mL ( r = 0.9994) for sulfur mustard and 0.25-20 μg mL ( r = 0.9897-0.9987) for nitrogen mustards, respectively.

Nitrogen Minimization in Hydrothermal Liquefaction Biocrude from Sewage Sludge with Green Extraction Solvents

“…DCM’s polarity allows it to interact more favorably with these compounds, leading to better extraction efficiency. , In addition to this, DCM can undergo nucleophilic substitution (SN2) reactions and has a higher affinity for polar and nonpolar compounds. This versatility enables DCM to efficiently extract a wide range of substances, including N and S compounds. , It has been reported that DCM is utilized to extract N and S compounds from aqueous solutions in sequential extraction processes after HTL of SS …”

“…This versatility enables DCM to efficiently extract a wide range of substances, including N and S compounds. 31,32 It has been reported that DCM is utilized to extract N and S compounds from aqueous solutions in sequential extraction processes after HTL of SS. 33 On the other hand, nonpolar solvents are suitable for certain extractions, but they may not effectively interact with polar N and S compounds.…”

A critical review on emerging photoactive porous materials for sulfide oxidation and sulfur mustard decontamination

“…Many materials have been employed to detoxify sulfur mustard and its analogous derivatives; in this context, owing to its attenable functionality, superior chemical and thermal stability, and enhanced porosity, POPs emerge as a judicious choice. 97 POPs are a class of advanced functional materials with structural tailorability, inherent porosity, and high flexibility, which have served for several applications like CO 2 capture, 98,99 CO 2 reduction to solar fuels, 100,101 biomass valorisation, 102,103 organic transformation reactions, 104,105 CO 2 fixation, 99 gas and liquid separation, 106 water purification, 107,108 energy storage, 109 chemo-and biosensing 110 and HD decontamination [111][112][113][114][115] etc. (Fig.…”

Ethanolysis of nitrogen mustards: A novel strategy for nitrogen mustard identification in environmental matrices by liquid chromatography–electrospray ionization–tandem mass spectrometry

“…Gas chromatography (GC) coupled with nitrogen-phosphorus detectors (NPDs) and GC-mass spectrometry methods have been reported mainly for the determination of intact NMs but also for the corresponding degradation products with and without derivatization in clinical and environmental matrices, organic solvents, vapor forms and hydrophobic matrices. [9][10][11][12][13][14][15][16][17][18][19] Reepmeyer et al derivatized HN2 with thiophenol to form a stable disubstituted derivative with a substantial UV chromophore. 20 Recently, a method was developed for the detection of half NM as a specific biomarker in plasma after NM exposure for verification by the CWC.…”