A C18 monolithic capillary column was utilized as the solid phase microextraction column to construct an in-tube SPME-HPLC system which was used to simultaneously extract and detect five phenoxy acid herbicides, including 2,4-dichlorophenoxyacetic acid (2,4-D), 2-(2-chloro)-phenoxy propionic acid (2,2-CPPA), 2-(3-chloro)-phenoxy propionic acid (2,3-CPPA), phenoxy propionic acid (PPA) and 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP). The operating parameters of the in-tube SPME-HPLC system, including the length of the monolithic column, the sampling flow rate, the sampling time, the elution flow rate and the elution time, had been investigated in detail. The optimized operating parameters of the in-tube SPME-HPLC system were as follow: the length of the monolithic column was 20 cm, the sampling flow rate was 0.04 mL/min, sampling time was 13 min; the elution flow rate was 0.02 mL/min, elution time was 5 min. Under the optimized conditions, the detection limits of the five phenoxy acid herbicides were as follows: 9 μg/L for PPA, 4 μg/L for 2,2-CPPA, 4 μg/L for 2,3-CPPA, 5 μg/L for 2,4-D, 5 μg/L for 2,4-DP. Compared with the HPLC method with direct injection, the combined system showed a good enrichment factors to the analytes. The recoveries of the five phenoxy acid herbicides were between 79.0% and 98.0% (RSD≤3.9%). This method was successfully used to detect the five phenoxy acid herbicides in water samples with satisfactory results.
WANG Jiabin,WU Fangling,ZHAO Qi. Synchronous extraction and determination of phenoxy acid herbicides in water by on-line monolithic solid phase microextraction-high performance liquid chromatography[J]. Chinese Journal of Chromatography, 2015, 33(8): 849-855.