Determination of Triazine Herbicides and Metabolites by Solid Phase Extraction with HPLC Analysis

Abstract

An efficient solid phase extractive preconcentration/separation method was developed for the trace determination of herbicides in aqueous samples using Amberlite XAD-4 resin as the adsorbent. The retained herbicides were eluted with methanol at a flow rate of 1.0 mL min⁻¹ and determined by HPLC-DAD (wavelength of 220 nm) using water (pH:4.7, phosphoric acid) and methanol (ratio 35:65) as the mobile phase with a flow rate of 1.0 mL min⁻¹. Quantitative recoveries of simazine, atrazine and its metabolities were achieved at optimized analysis conditions that included 0.75 g of resin; a pH of 3.0; an eluent volume of 3.0 mL; an eluent flow rate of 1.0 mL min⁻¹; and a sample flow rate of 4.0 mL min⁻¹. The limits of detection, preconcentration factor, and linear ranges for the herbicides were 0.084–0.121 µgL⁻¹, 1000, and 0.5–20 mg L⁻¹, respectively. The performance of the method was evaluated by analysis of spiked water samples. The recoveries of simazine, atrazine and their metabolities were found to be quantitative (99.6–104.8%) with RSDs of 2.2–4.8% and 2.8–4.7% for intra-day and inter-day precision, respectively. The proposed method was successfully applied for trace determination of studied analytes in waste water, apple juice, and red wine samples.

Keywords:

• Herbicide
• HPLC
• Metabolites
• Preconcentration
• SPE

Acknowledgments

We are grateful for the financial support of the Scientific Research Projects Unit at Pamukkale University (Project No. 2011 BSP 032). Moreover, the authors acknowledge the Nilgun ELYAS laboratory supervisor of the Denizli Environment Quality Laboratory (DENCEV) for domestic waste water and the Ilker DOGRUL Laboratory of Denizli Organized Industrial Zone Central Wastewater Treatment Plant for industrial waste water.

Notes

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SPE-GC-MS-SIM, Solid Phase Extraction Gas Chromatography- Mass Spectrometry- Selective Ion Monitoring; SPE-GC-MS, Solid Phase Extraction Gas Chromatography- Mass Spectrometry; SPE-GC-MS/MS, Solid Phase Extraction Gas Chromatography- Tandem Mass Spectrometry; HPLC-DAD, High-Performance Liquid Chromatography- Diode-Array Detection; micro-LC-UV, micro- Liquid Chromatography-Ultra Viyole Spectrophotometry; GC-MS/MS, Gas Chromatography- Tandem Mass Spectrometry; LC-MS/MS, Liquid Chromatography- Tandem Mass Spectrometry; SPE-LC-ESI-MS/MS, Solid Phase Extraction- Liquid Chromatography- Electrospray Ionization- Tandem Mass Spectrometry; HPLC-UV, High-Performance Liquid Chromatography-Ultra Viyole Spectrophotometry; SPE-HPLC-DAD, Solid Phase Extraction -High-Performance Liquid Chromatography- Diode-Array Detection.