Analytical and Bioanalytical Chemistry

, Volume 391, Issue 1, pp 97–116 | Cite as

LC-MS-based procedures for monitoring of toxic organophosphorus compounds and verification of pesticide and nerve agent poisoning

  • Harald JohnEmail author
  • Franz Worek
  • Horst Thiermann


Organophosphorus compounds (OPCs) are used worldwide as, e.g., flame retardants, plasticizers, and pesticides and remaining stockpiles of OPC nerve agents are present in military arsenals. These OPCs exhibit acute and potential chronic toxicity to man, the environment, and biota thus emphasizing the need for efficient analytical procedures to monitor potential risk to health. Therefore, this review discusses LC-MS-based procedures for OPC detection, addressing sample preparation, separation, ionization, and detection in comprehensive detail. For sample preparation conventional liquid-liquid extraction (LLE) and diverse solid-phase extraction (SPE) procedures are still used most frequently. Nevertheless, during the last three years a number of sophisticated novel methods have been introduced. Solid-phase microextraction (SPME), stir-bar-sorptive extraction (SBSE), membrane-assisted solvent extraction (MASE), and specifically designed molecularly imprinted polymers (MIP) exhibit high potential for frequent use in the future. Additional emphasis in this review is dedicated to the quite young history and current progress in ionization and MS detection of OPCs. The number of relevant published LC-MS reports has tripled in the last five years. This is especially due to the proliferating use of electrospray ionization (ESI), nowadays an indispensable and reliable tool for LC-MS coupling. LC-MS is becoming an appropriate complementary or replacement method for the more traditional GC-MS methods, and not only for non-volatile, hydrophilic, and ionic OPCs. The last section of this review covers recent approaches for verification of OPC poisoning. LC-MS-MS detection of phosphylated peptides generated from inhibited circulating serum butyrylcholinesterase (BChE) by valuable proteomics techniques enables proof of intoxication on the molecular level. Therefore, this review gives a comprehensive overview on the status quo of LC-MS-based OPC analysis in respect of both technical progress and relevant applications.


Monitoring and verification


Biomonitoring Flame retardants LC-MS Nerve agents Organophosphorus compounds Pesticides Verification 







Atmospheric pressure chemical ionization


Accelerated solvent extraction






Collision-induced dissociation


Cyclohexyl methylphosphonic acid


Diethyl phosphoric acid


Diethyl thiophosphoric acid


Dimethyl phosphoric acid


Dimethyl thiophosphoric acid


Ethyl acetate


Ethyl phosphoric acid


Electrospray ionization


Formic acid


Fast atom bombardment


Isopropyl methylphosphonic acid


Liquid-liquid extraction


Lower limit of quantification

log P

Logarithm of octanol/water partition coefficient


Membrane-assisted solvent extraction


Molecularly imprinted polymers


Methylphosphonic acid


Pinacolyl methylphosphonic acid


Organophosphorus compound


Organophosphorus nerve agent


Organophosphorus pesticide


Particle beam ionization


Restricted-access material




Stir-bar-sorptive extraction


Solid-phase extraction


Solid-phase microextraction


Trifluoroacetic acid




Thermospray ionization


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Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  1. 1.Bundeswehr Institute of Pharmacology and ToxicologyMunichGermany

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