Development of on-line monolith-based in-tube solid phase microextraction for the sensitive determination of triazoles in environmental waters

In this work, a convenient and sensitive method for the determination of triazoles in environmental waters was developed by on-line combining in-tube solid phase microextraction (IT-SPME) and high performance liquid chromatography with diode array detector (HPLC-DAD). To extract triazoles effectively, poly (4-vinyl pyridine-co-ethylene dimethacrylate) monolith was in-situ fabricated and utilized as the extraction phase of IT-SPME. A series of key extraction parameters including desorption solvent, sample volume, adsorption and desorption flow rate, pH value and ionic strength in sample matrix were optimized thoroughly. Under the most favorable conditions (volume of sample, 6.0 mL; adsorption flow rate, 0.2 mL/min; desorption solvent, 80.0 µL mixture of ACN/water (70/30, v/v); desorption flow rate, 50.0 µL/min; sample pH value, 8.0; ionic strength did not be adjusted), the developed monolith-based IT-SPME could extract target analytes effectively and expected analytical merits were achieved. The limits of detection (S/N = 3) and limits of quantification (S/N = 10) were in the ranges of 0.014-0.031 µg/L and 0.11-0.074 µg/L, respectively. Satisfactory method reproducibility was obtained by intra-day and inter-day precisions, with relative standard deviations (RSDs) lower than 10%. The optimized IT-SPME-HPLC-DAD method was then applied to detect triadimenol, triazolone and hexaconazole in water samples including lake, river and sewage waters. The spiked recoveries were 78.9-106% and the RSDs were in the range of 0.2-7.2%. The results well evidence that the proposed method is convenient, accurate, sensitive, practical and environmentally friendly for the determination of triazoles in environmental waters.