In the present study, an efficient, robust, and reliable air–assisted liquid–liquid microextraction procedure was introduced based on a “water-lean” solvents for the extraction and preconcentration of phenolic compounds from spring water and petrochemical, Songun mine, and municipal wastewater samples. For this purpose, various hydrophobic water-lean solvents composed of organic solvents consisting of carbon tetrachloride, dichloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, and chloroform with amines including n-butylamine, di-n-butylamine, iso-propylamine, n-hexylamine, diethylamine, pyridine, aniline, toluidine, and benzylamine) were prepared and they were used as the new extraction media. The selected compounds (phenol, 1-naphthol, 2-naphthol, 4- chlorophenol, o-cresol, 2-nitrophenol, and 2-nitroso-1-naphthol) were extracted from sample solution containing sodium chloride (5 %, w/v) using 200 µL of a water-lean solvent composed of dichloromethane: butylamine (1:1) by performing the sucking/injection cycles for four times. The effect of several parameters on the extraction efficiency of the method, consisting of type and volume of water-lean solvent, extraction numbers, pH, and ionic strength, were examined and optimized by “one-variable-at-one-time” strategy. High enrichment factors (315–420), respectable extraction recoveries (63–84 %), low limits of detection (0.23–0.56 ng mL−1) and quantification (0.77–1.86 ng mL−1), and broad linearity of the calibration curve (1.86–500 ng mL−1) demonstrated satisfactory performance of the present approach. The relative standard deviation for the extraction of 50 and 100 ng mL−1 of each phenol (n = 6) were ≤ 6.3 % for intra- and inter-day precisions. Eventually, the proposed method was efficaciously performed for extraction and determination of the selected analytes in various water and wastewater samples and phenol and 4-chlorophenol were found in the samples at ng mL−1 level.
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