Automation in quantifying phenoxy herbicides and bentazon in surface water and groundwater using novel solid phase extraction and liquid chromatography tandem mass spectrometry.
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abstract
The occurrence of phenoxy herbicides is a financial and regulatory concern for drinking water treatment plants. This paper presents a new method of quantification for nine phenoxy-acids and bentazon in different water samples using liquid chromatography tandem mass spectrometry (LC-MS/MS). The method is based on an automated solid phase extraction (SPE) process that applied hydrophilic modified polystyrene and divinylbenzene cartridges at low pH (<2.0). Main advantages of the presented method include the reduced consumption of organic solvent in extraction and the fully automated sample pre-concentration. The method is thus more environmentally-friendly. In the quantification step, five stable isotopically labelled analogues were used as internal standards to account for the losses during sample preparation and to calibrate the ion source response under the mass spectrometric detection. The method was optimized in terms of sample preparation and subsequent LC-MS/MS separation to obtain reliable measurement of the analyte concentration during real sample analysis. The method quantification limit was between 1.5 and 10.0ng/L for target compounds in surface water and groundwater samples. The method was validated at three fortification levels between 10.0 and 1000ng/L, and the results showed fit-for-purpose recovery with appropriate precision at low concentration levels. The method was also utilized to analyse thirty-two actual water samples from different sources. Forty percent of the analysed samples contained detectable level of herbicides, ranging from 1.91 to 40.5ng/L. The concentrations of targeted herbicides in our study were comparable to those found in water samples in other regions of world.