Detection of chlordecone by liquid chromatography with tandem mass spectrometryChlordecone (decachlorooctahydro-1,3, 2-metheno-2H-cyclobuta [c,d]pentalen-2-one) is an organo-chlorine insecticide that was formerly used extensively.
1The compound is a member of the persistent organic pollutants that exhibit remarkably long half-lives in the environment, and it is well known that chlordecone shows various toxicities such as arrest of sperm maturation, 2 blocking of reproductive function, 3 and a variety of estrogen-like effects on the female reproductive system in birds and mammals. 4 Therefore, it is very important to understand the chlordecone concentration in various environments.In general, chlordecone is determined by gas chromatography with electron capture detection (GC/ECD). 5 However, in order to apply an appropriate method to the analysis of chlordecone in various environmental media and matrices, it is important to develop a novel analytical method to complement the methods based on GC. We have developed an analytical method for chlordecone using liquid chromatography with tandem mass spectrometry (LC/MS/MS). The LC/ MS/MS technique has the potential to simplify the analytical pretreatment, and to provide rapid confirmation of chlordecone in environmental samples.Chlordecone was purchased from Wako Pure Chemical Industries (Osaka, Japan). A stock solution at a concentration of 1000 mg/mL was prepared by dissolution of chlordecone in methanol. The solutions were stored in the dark. Working standards were prepared on a daily basis by dilution of the stock solution with methanol. Chlordecone-13 C 8 , used as an internal standard, was obtained from Cambridge Isotope Laboratories Inc. (Andover, USA). Five mL of the internal methanol solution (0.1 mg/mL) was added to the chlordecone standard solutions (1.0 mL).The LC/MS/MS analysis was performed using a MDS-Sciex API 3000 system (Applied Biosystems). Ionization of chlordecone was achieved by electrospray (ESI-MS) in the negative ion mode. All the interface parameters were optimized by infusing a standard solution (0.1 mg/mL) of the analytes. The final electrospray conditions were as follows: nitrogen curtain gas, 6 psi; ion spray voltage, À4500 V; declustering potential, À81 V. The full-scan single-quadrupole mass spectra were obtained in the range m/z 400-700 at a scan rate of 1 scan/s. The product-ion mass spectrum of the ion (m/z 507) was acquired in the range m/z 10-520 at a scan rate of 1 scan/s. The collision energies were À28 and À32 eV for chlordecone and the internal standard, respectively. The LC/MS/MS acquisition was performed in the multiple reaction monitor (MRM) mode by following the reactions m/z 507 ! 427, characteristic of chlordecone, and m/z 515 ! 434, characteristic of the internal standard, chlordecone-13 C 8 . Liquid chromatography was conducted using an 1100 series (Agilent) separation module interfaced to the API 3000 system. A Develosil C30-UG-5 column (Nomura Chemicals; 5 mm particle size, 2.0 mm i.d. Â 150 mm) was used for the LC sepa...