Parallel artificial liquid membrane extraction of organophosphorus nerve agent degradation products from environmental samples

Abstract

An emerging miniaturized high-throughput microextraction technique named Parallel artificial liquid membrane extraction (PALME) was, for the first time, investigated for the extraction of polar alkyl methylphosphonic acids (AMPAs) that are the degradation products of organophosphorus nerve agents. The effect of the key-parameters of the extraction method (nature of the membrane, of the extraction solvent, of the pH values of both donor and acceptor phases, agitation speed, extraction time, temperature and ionic strength) on the extraction recoveries was studied in spiked pure water samples. This led to extraction recoveries in the range of 25-102% for the 5 targeted analytes from water with enrichment factors in the range of 4.50-42.75. The developed PALME-LC-MS/MS method was first evaluated with spiked pure water. LOQs (S/N ≥ 10) were in the range of 0.009-1.141 ng mL^-1, linearity above 0.9973 for all the AMPAs and with RSD values below 11%. This method was then applied on simulated waste water, river water and aqueous soil extracts. The achieved LOQs were in the range of 0.011-1.210, 0.013-1.196 and 0.016-6.810 ng mL^-1, respectively. A detailed comparison of the performances of this PALME method with those of a previously developed hollow fiber liquid-phase microextraction methods already applied to AMPAs was done thus allowing to demonstrate the easy transfer of methods from HF-LPME to PALME. Moreover, the high-throughput potential of PALME was revealed since 192 samples were processed in parallel during 120 min (37.5 s/sample).

Keywords: Alkyl methylphosphonic acids; Chemical warfare agent degradation products; Environmental samples; LC-MS/MS analysis; Parallel artificial liquid membrane extraction.