Three-phase hollow fiber liquid-phase microextraction of organophosphorous nerve agent degradation products from complex samples

Degradation products of chemical warfare agents are considered as important environmental and biological markers of chemical attacks. Alkyl methylphosphonic acids (AMPAs), resulting from the fast hydrolysis of nerve agents, such as sarin and soman, and the methylphosphonic acid (MPA), final degradation product of AMPAs, were determined from complex matrices by using an emergent and miniaturized extraction technique, the hollow fiber liquid-phase microextraction (HF-LPME), before their analysis by liquid chromatography coupled to mass spectrometry (LC–MS). After studying different conditions of separation in the reversed phase LC–MS analysis, the sample treatment method was set up.The three-phase HF-LPME was carried out by using a porous polypropylene (PP) hollow fiber impregnated with 1-octanol that separates the donor and acceptor aqueous media. Various extraction parameters were evaluated such as the volume of the sample, the effect of the pH and the salt addition to the sample, the pH of the acceptor phase, the extraction temperature, the stirring speed of the sample, the immersion time in the organic solvent and the time of extraction. The optimum conditions were applied to the determination of MPA and five AMPAs in real samples, such as surface waters and urine. Compounds were extracted from a 3 mL acidified sample into only 6 μL of alkaline water without any other pretreatment of the complex matrices. Enrichment factors (EFs) higher than 170 were obtained for three less polar AMPAs. Limits of quantification (LOQs) in the 0.013–5.3 ng mL−1 range were obtained after microextraction of AMPAs from river water and in the range of 0.056–4.8 ng mL−1 from urine samples with RSD values between 1 and 9%.

► High potential of HF-LPME applied to reduced size samples.
► High enrichment factor for the extraction of polar compounds from water and urine.
► Quantitative extraction of AMPAs from surface waters and urine samples.
► High sensitivity for the LC/MS analysis of AMPAs without any derivatization step.