Oxidation as a Pre-Step in Determination of Organophosphorus Compounds by the AChE-Tls Bioassay
Mojca Bavcon Kralj, Polonca Trebše, Mladen FrankoLaboratory for Environmental Research, Nova Gorica Polytechnic, Vipavska 13,
P. O. Box 301, 5001-SI,
Nova Gorica, Slovenia
Abstract
The oxidation efficiency of N-bromosuccinimide (NBS),
hypochloride and other oxidants such as m-CPBA, Oxone, CAN, iodine water,
hydrogen peroxide in aqueous solution and juice samples spiked with four model
thio-organophosphorus compounds (thio-OPs): azinphos-methyl, chlorpyrifos,
diazinon and malathion, was studied. The complete conversion into oxons was
noticed within five minutes in case of NBS, a partial conversion in case of
sodium hypochlorite, and no oxo-products were observed using other oxidants.
Since the NBS is efficient in acidic conditions and hypochlorite in alkaline
media, the hydrolysis during the oxidation process can be significantly avoided
using appropriate pHs. All oxidation experiments were verified using GC-MS
analysis. Compounds of interest were quantified by using standard solutions of
thio-OPs and identification of formed oxo-OPs was based on MS spectra. The
formed oxo-analogs were detected using AChE-bioassay with TLS detection, which
enabled determination of parent thio-compounds at ppb levels. With a rapid (5
min) oxidizing pre-step the AChE-bioassay can serve as a fast pre-screening test
(15 min) to identify samples that contain AChE inhibitors, including the
thio-OPs.
Key words: organophosphorus pesticides, oxidation, AChE-TLS bioassay