Dispersive liquid–liquid microextraction combined with gas chromatography-flame photometric detection: Very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water

Abstract

A new method was used for the extraction of organophosphorus pesticides (OPPs) from water samples: dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography-flame photometric detection (GC-FPD). In this extraction method, a mixture of 12.0 μL chlorobenzene (extraction solvent) and 1.00 mL acetone (disperser solvent) is rapidly injected into the 5.00 mL water sample by syringe. Thereby, a cloudy solution is formed. In fact, the cloudy state is because of the formation of fine droplets of chlorobenzene, which has been dispersed among the sample solution. In this step, the OPPs in water sample are extracted into the fine droplets of chlorobenzene. After centrifuging (2 min at 5000 rpm), the fine droplets of chlorobenzene are sedimented in the bottom of the conical test tube (5.0 ± 0.3 μL). Sedimented phase (0.50 μl) is injected into the GC for separation and determination of OPPs. Some important parameters, such as kind of extraction and disperser solvent and volume of them, extraction time, temperature and salt effect were investigated. Under the optimum conditions, the enrichment factors and extraction recoveries were high and ranged between 789–1070 and 78.9–107%, respectively. The linear range was wide (10–100 000 pg/mL, four orders of magnitude) and limit of detections were very low and were between 3 to 20 pg/mL for most of the analytes. The relative standard deviations (RSDs) for 2.00 μg/L of OPPs in water with internal standard were in the range of 1.2–5.6% ( n = 5) and without internal standard were in the range of 4.6–6.5%. The relative recoveries of OPPs from river, well and farm water at spiking levels of 50, 500 and 5000 pg/mL were 84–125, 88–123 and 93–118%, respectively. The performance of proposed method was compared with solid-phase microextraction (SPME) and single drop microextraction. DLLME is a very simple and rapid (less than 3 min) method, which requires low volume of sample (5 mL). It also has high enrichment factor and recoveries for extraction of OPPs from water.