Multiple headspace solid-phase microextraction of ethyl carbamate from different alcoholic beverages employing drying agent based matrix modification

Multiple headspace solid-phase microextraction (MHS-SPME) combined with gas chromatography-nitrogen phosphorus detector is proposed to determine the toxic contaminant ethyl carbamate (EC) in various alcoholic beverages after matrix modification. The remarkable feature of this method is that matrix effect, which commonly appears in SPME-based analysis, is avoided by determining the total amount of the analyte in the sample. To increase the sensitivity of the method, a novel polyethylene glycol/hydroxy-terminated silicone oil fiber was developed by sol–gel technique and applied for the analysis. Owing to the high polarity and hydrophilia of EC, an important problem still remains because the adsorption by sample matrix causes low transport of EC to the headspace and thus invalidates MHS-SPME for quantification. Mixing with anhydrous sodium sulphate, the sensitivity of the method can be improved. A Taguchi's L16 (45) orthogonal array design was employed to evaluate potentially significant factors and screen the optimum conditions for MHS-SPME of EC. Under the optimized conditions, limit of detection of 0.034 mg L−1 was obtained. Relative standard deviation of replicate samples (n = 6) was 2.19%. The proposed method was linear in the range of 0.04–100 mg L−1, and the coefficient of determination was 0.9997. The method was used to determine EC in various alcoholic beverages. The concentrations obtained were compared with those obtained by standard addition method and no statistically significant differences were observed.