High-performance liquid chromatography with paired ion electrospray ionization (PIESI) tandem mass spectrometry for the highly sensitive determination of acidic pesticides in water

• A new HPLC–MS/MS method based on paired ion electrospray ionization (PIESI) has been developed to determine acidic pesticides at ultratrace levels.
• This method provides orders of magnitude greater sensitivity than in the usual negative mode.
• Sub-picogram level LODs were obtained using optimal ion-pairing reagent.
• Trace amounts of pesticides in water samples were determined by using this method.

A novel method based on the paired ion electrospray ionization (PIESI) mass spectrometry has been developed for determination of acidic pesticides at ultratrace levels in surface and ground waters. The proposed approach provides greatly enhanced sensitivity for acidic pesticides and overcomes the drawbacks of the less sensitive negative ion mode ESI-MS. The limits of detection (LODs) of 19 acidic pesticides were evaluated with four types of dicationic ion-pairing reagent (IPR) in both single ion monitoring (SIM) and selected reaction monitoring (SRM) mode. The LOD of 19 pesticides obtained with the use the optimal dicationic ion-pairing reagent ranged from 0.6 pg to 19 pg, indicating the superior sensitivity provided by this method. The transition pathways for different pesticide-IPR complexes during the collision induced dissociation (CID) were identified. To evaluate and eliminate any matrix effects and further decrease the detection limits, off-line solid-phase extraction (SPE) was performed for DI water and a river water matrix spiked with 2000 ng L−1 and 20 ng L−1 pesticides standards respectively, which showed an average percent recovery of 93%. The chromatographic separation of the acidic pesticides was conducted by high-performance liquid chromatography (HPLC) using a C18 column (250 mm × 2.1 mm) in the reversed phase mode using linear gradient elution. The optimized HPLC–PIESI-MS/MS method was utilized for determination of acidic pesticide at ng L−1 level in stream/pond water samples. This experimental approach is 1–3 orders of magnitude more sensitive for these analytes than other reported methods performed in the negative ion mode.

Figure optionsDownload as PowerPoint slide