Trace determination of primary nerve agent degradation products in aqueous soil extracts by on-line solid phase extraction–liquid chromatography–mass spectrometry using ZrO2 for enrichment

•ZrO2 has strong affinity for the deprotonated alkyl methylphosphonic acids.•ZrO2 was combined with a reversed phase separation column in on-line SPE–LC–MS.•Alkyl methylphosphonic acids were eluted from ZrO2 by 15mM ammonium acetate.•Humic compounds were eluted from ZrO2 with H2O/acetonitrile (60/40...

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Bibliographic Details
Published in:	Journal of Chromatography A Vol. 1329; pp. 90 - 97
Main Authors:	Røen, Bent Tore, Sellevåg, Stig Rune, Dybendal, Kjersti E., Lundanes, Elsa
Format:	Journal Article
Language:	English
Published:	Amsterdam Elsevier B.V 14-02-2014 Elsevier Elsevier Science
Subjects:	Alkyl methylphosphonic acid Analysis methods Analytical chemistry Applied sciences Chemical Warfare Agents - analysis Chemical Warfare Agents - chemistry Chemistry Chromatographic methods and physical methods associated with chromatography Chromatography Chromatography, Liquid - methods Degradation Exact sciences and technology Lewis base Mass Spectrometry - methods Nerves On-line SPE–LC–MS On-line systems Organophosphorus Compounds - chemistry Other chromatographic methods Pollution Porosity Soil Soil (material) Soil and sediments pollution Solid Phase Extraction - methods Titanium dioxide Zirconium - chemistry Zirconium dioxide On-line SPE–LC–MS Alkyl methylphosphonic acid Zirconium dioxide Lewis base Solid phase extraction Chemical analysis On line Zirconium IV Oxides HPLC chromatography Soil pollution Phosphorus Organic compounds Electrospray Chemical enrichment Chemical warfare agent Sample preparation War gas Adsorbent Quantitative analysis Trace analysis Validation Coupled method Toxin Soils Reversed phase chromatography On-line SPE-LC-MS Neurotoxin Aqueous solution Degradation product Mass spectrometry
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Summary:	•ZrO2 has strong affinity for the deprotonated alkyl methylphosphonic acids.•ZrO2 was combined with a reversed phase separation column in on-line SPE–LC–MS.•Alkyl methylphosphonic acids were eluted from ZrO2 by 15mM ammonium acetate.•Humic compounds were eluted from ZrO2 with H2O/acetonitrile (60/40) at pH 10. A method for determination of the primary nerve agent degradation products ethyl-, isopropyl-, isobutyl-, cyclohexyl- and pinacolyl methylphosphonic acid in aqueous soil extracts has been developed utilizing on-line solid phase extraction-liquid chromatography and mass spectrometry (SPE–LC–MS). Four different stationary phases (ZrO2, TiO2, polymeric mixed mode anion exchange and porous graphitic carbon) were investigated for their suitability as SPE materials in the on-line SPE–LC–MS setup. Zirconium dioxide was chosen due to its high affinity for the alkyl methylphosphonic acids (AMPAs), and its compatibility with LC–MS. Aqueous soil extracts were acidified with 0.1% acetic acid and aliquots of 300μL were injected on a 2mm×10mm ZrO2 column. Separation of the analytes was performed on a reversed phase column with acetonitrile/water gradient and 15mM ammonium acetate. Method validation was performed with the analytes added to an aqueous extract of a loam soil, and the AMPAs could be determined at concentrations as low as 0.05–0.5μgL−1. The method was linear (R2>0.995) from the limit of quantification (LOQ) to 100×LOQ, and the within assay repeatability was below 10% and 5% relative standard deviation at LOQ and 50×LOQ, respectively. The developed method was employed for determination of the AMPAs which had been added to the aqueous extracts of five different soil types from cultivated and uncultivated areas. The obtained recoveries showed that the analytes could be determined at the sensitivities achieved in the method validation in four of the extracts. For the first time, we have demonstrated a method capable of detecting primary nerve agent degradation products at sub ppb levels in the aqueous extracts of various soils. The method requires no sample preparation after soil extraction other than pH adjustment of the aqueous extract.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	0021-9673 1873-3778
DOI:	10.1016/j.chroma.2014.01.004