Dispersive derivatization liquid–liquid extraction of degradation products/precursors of mustards and V-agents from aqueous samples

A new derivatization and extraction technique termed as dispersive derivatization liquid–liquid extraction (DDLLE) speeds up the analysis process by removing the requirement for drying of the sample. The derivatization process takes place at the interface between the analyte containing aqueous phase and derivatization agent laden organic phase. The organic phase is highly dispersed using disperser solvent so that the total surface area is large. The derivatizing agent used is 1-(heptafluorobutyryl)imidazole and the resulting heptafluorobutyryl (HFB) derivatized analytes are partitioned into the organic phase. In addition to reduced sample preparation time, for some of the analytes, the HFB derivatives provide better spectral differentiation between isomers than conventional trimethylsilyl (TMS) derivatives. Method parameters for the DDLLE, such as extraction, and disperser solvent and their volume, type and amount of base, amount of heptafluorobutyrylimidazole and extraction time were optimized on diisopropylaminoethanol (DiPAE), ethyldiethanolamine (EDEA), triethanolamine (TEA) and thiodiglycol (TDG). The DDLLE was also used on various real world samples, which also includes few OPCW organized proficiency test and a spiked urine sample. The observed limit of detection (LOD) with 1 mL of sample for DDLLE in full scan with AMDIS was 10 ng/mL and with methane chemical ionization, multiple reaction monitoring (MRM) was 100 pg/mL, i.e., 100 fg on-column.