title: Automated on-line in-tube solid-phase microextraction followed by liquid chromatography/electrospray ionization-mass spectrometry for the determination of chlorinated phenoxy acid herbicides in environmental waters.
abstract: A method for the determination of six chlorinated phenoxy acid herbicides in river water was developed using in-tube solid-phase microextraction (SPME) followed by liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS). In-tube SPME is an extraction technique for organic compounds in aqueous samples, in which analytes are extracted from a sample directly into an open tubular capillary by repeated draw/eject cycles of the sample solution. Simple mass spectra with strong signals corresponding to [M-H]- and [M-RCOOH]- were observed for all herbicides tested in this study. The best separation of these compounds was obtained with a C18 column using linear gradient elution with a mobile phase of acetonitrile-water containing 5 mmol l-1 dibutylamine acetate (DBA). To optimize the extraction of herbicides, several in-tube SPME parameters were examined. The optimum extraction conditions were 25 draw/eject cycles of 30 microliters of sample in 0.2% formic acid (pH 2) at a flow rate of 200 microliters min-1 using a DB-WAX capillary. The herbicides extracted by the capillary were easily desorbed by 10 microliters acetonitrile. Using in-tube SPME-LC/ESI-MS with time-scheduled selected ion monitoring, the calibration curves of herbicides were linear in the range 0.05-50 ng ml-1 with correlation coefficients above 0.999. This method was successfully applied to the analysis of river water samples without interference peaks. The limit of quantification was in the range 0.02-0.06 ng ml-1 and the limit of detection (S/N = 3) was in the range 0.005-0.03 ng ml-1. The repeatability and reproducibility were in the range 2.5-4.1% and 6.2-9.1%, respectively.
authors.affiliation: Kansai Branch Office, Yokogawa Analytical Systems Inc., 3-3-11 Kinryo Bld., Niitaka, Yodogawa, Osaka 532-0033, Japan. masahiko_takino@agilent.com
authors.forename: M
authors.initials: M
authors.lastname: Takino
authors.forename: S
authors.initials: S
authors.lastname: Daishima
authors.forename: T
authors.initials: T
authors.lastname: Nakahara
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods; D006540:Herbicides / Q000032:analysis* / Q000302:isolation & purification; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000302:isolation & purification
chemical_list: D006540:Herbicides; D014874:Water Pollutants, Chemical