Abstract
A novel method for the simultaneous separation and determination of four benzimidazole fungicides (i.e., carbendazim, fuberidazole, thiophanate-methyl and thiophanate) in high salinity samples was developed by using salting-out assisted liquid–liquid extraction (SALLE) via water-miscible acetonitrile as the extractant coupled with high-performance liquid chromatography. Box–Behnken design and response surface were employed to assist the optimization of SALLE conditions, including volume of salting-out solvent, the pH of sample solution and salting-out solvent as variable factors. The optimal salting-out parameters were obtained as follows: 2mL of acetonitrile was added to 2mL of sample solution with pH=4 and then 2mL salting-out solvent containing 5molL−1 sodium chloride at a pH of 7 was added to the solution for extraction. This procedure afforded a convenient and cost-saving operation with good cleanup ability for the benzimidazole fungicides, such as good linear relationships (R>0.996) between peak area and concentration from 2.5ngmL−1 to 500ngmL−1, low limits of detection between 0.14ngmL−1 and 0.38ngmL−1 and the intra-day precisions of retention time below 1.0%. The method recoveries obtained at fortified three concentrations for three seawater samples ranged from 60.4% to 99.1%. The simple, rapid and eco-benign SALLE based method proved potentially applicable for trace benzimidazole fungicides analysis in high salinity samples.
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