Vortex‐assisted surfactant‐enhanced‐emulsification liquid–liquid microextraction of biogenic amines in fermented foods before their simultaneous analysis by high‐performance liquid chromatography

A simple, rapid, sensitive, and environmentally friendly method, based on modified dispersive liquid–liquid microextraction coupled with high‐performance liquid chromatography was developed for the simultaneous determination of five biogenic amines in fermented food samples. Biogenic amines were derivatized with 9‐fluorenylmethyl chloroformate, extracted by vortex‐assisted surfactant‐enhanced emulsification liquid–liquid microextraction, and then analyzed by high‐performance liquid chromatography. Five biogenic amine compounds were separated within 30 min using a C₁₈ column and gradient elution with acetonitrile and 1% acetic acid. Factors influencing the derivatization and extraction efficiency such as type and volume of extraction solvent, type, and concentration of surfactant, pH, salt addition, and vortex time were optimized. Under the optimum conditions, the method provided the enrichment factors in the range of 161–553. Good linearity was obtained from 0.002–0.5 mg/L for cadaverine and tyramine, 0.003–1 mg/L for tryptamine and histamine, and 0.005–1 mg/L for spermidine with coefficient of determination (R²) > 0.992. The limits of detection ranged from 0.0010 to 0.0026 mg/L. The proposed method was successfully applied to analysis of biogenic amines in fermented foods such as fermented fish (plaa‐som), wine and beer where good recoveries were obtained in the range of 83.2–112.5%     

Determination of N‐nitrosamines in cosmetic products by vortex‐assisted reversed‐phase dispersive liquid–liquid microextraction and liquid chromatography with mass spectrometry

A new analytical method for the simultaneous determination of trace levels of seven prohibited N‐nitrosamines (N‐nitrosodimethylamine, N‐nitrosoethylmethylamine, N‐nitrosopyrrolidine, N‐nitrosodiethylamine, N‐nitrosopiperidine, N‐nitrosomorpholine, and N‐nitrosodiethanolamine) in cosmetic products has been developed. The method is based on vortex‐assisted reversed‐phase dispersive liquid–liquid microextraction, which allows the extraction of highly polar compounds, followed by liquid chromatography with mass spectrometry. The variables involved in the extraction process were studied to obtain the highest enrichment factor. Under the selected conditions, 75 μL of water as extraction solvent was added to 5 mL of n‐hexane sample solution and assisted by vortex mixing during 30 s to form the cloudy solution. The method was successfully validated showing good linearity (0.5–50 ng/mL), enrichment factors up to 65 depending on the target compound, limits of detection values of 1.8–50 ng/g, and good repeatability (RSD < 9.8%). Finally, the proposed method was applied to different cosmetic samples. Quantitative relative recovery values (80–113%) were obtained, thus showing that matrix effects were negligible. The achieved analytical features of the proposed method, besides of its simplicity and affordability, make it useful to perform the quality control of cosmetic products to ensure the safety of consumers.     

Ionic‐liquid‐based dispersive liquid–liquid microextraction combined with magnetic solid‐phase extraction for the determination of aflatoxins B1, B2, G1, and G2 in animal feeds by high‐performance liquid chromatography with fluorescence detection

A novel two‐step extraction technique combining ionic‐liquid‐based dispersive liquid–liquid microextraction with magnetic solid‐phase extraction was developed for the preconcentration and separation of aflatoxins in animal feedstuffs before high‐performance liquid chromatography coupled with fluorescence detection. In this work, ionic liquid 1‐octyl‐3‐methylimidazolium hexafluorophosphate was used as the extractant in dispersive liquid–liquid microextraction, and hydrophobic pelargonic acid modified Fe₃O₄ magnetic nanoparticles as an efficient adsorbent were applied to retrieve the aflatoxins‐containing ionic liquid. Notably, the target of magnetic nanoparticles was the ionic liquid rather than the aflatoxins. Because of the rapid mass transfer associated with the dispersive liquid–liquid microextraction and magnetic solid phase steps, fast extraction could be achieved. The main parameters affecting the extraction recoveries of aflatoxins were investigated and optimized. Under the optimum conditions, vortexing at 2500 rpm for 1 min in the dispersive liquid–liquid microextraction and magnetic solid‐phase extraction and then desorption by sonication for 2 min with acetonitrile as eluent. The recoveries were 90.3–103.7% with relative standard deviations of 3.2–6.4%. Good linearity was observed with correlation coefficients ranged from 0.9986 to 0.9995. The detection limits were 0.632, 0.087, 0.422 and 0.146 ng/mL for aflatoxins B₁, B2, G1, and G2, respectively. The results were also compared with the pretreatment method carried out by conventional immunoaffinity columns.     

Separation and pre‐concentration of glucocorticoids in water samples by ionic liquid supported vortex‐assisted synergic microextraction and HPLC determination

We have developed a synergic microextraction procedure based on ionic liquid for the pre‐concentration and determination of glucocorticoids in water samples. Using nonionic surfactant Triton X‐100 (TX‐100) as synergic reagent, 1‐butyl‐3‐methylimidazolium hexa‐fluorophosphate accomplished extraction rapidly without heating in water bath. One key property of ionic liquids that highlights their potential is their wide liquid temperature range. The improved extraction was named as ionic liquid supported vortex‐assisted synergic microextraction. Compared with the traditional liquid–liquid extraction and cloud point extraction, ionic liquid supported vortex‐assisted synergic microextraction was accomplished in 8 min with considerably high recovery. The proposed method greatly improved the sensitivity of HPLC for the determination of glucocorticoids. The results obtained indicated a good linearity with the correlation coefficient of 0.997 over the range of 0.6–300 ng/mL and high sensitivity with LODs of 4.11, 9.19, and 7.50 ng/mL for hydrocortisone butyrate, beclomethasone dipropionate, and nandrolone phenylpropionate, respectively. The RSD of the method was 1.57–1.81% (n = 6) with enrichment factor of 99.85, and good recovery (≥97.24%). The method was successfully applied to the determination of glucocorticoids in mineral water, water of Dianchi lake, and tap water samples.     

Vortex‐assisted liquid–liquid microextraction of strontium from water samples using 4′,4″(5″)‐di‐(tert‐butylcyclohexano)‐18‐crown‐6 and tetraphenylborate

A vortex‐assisted liquid–liquid microextraction method was developed for the chromatographic determination of strontium in aqueous samples. In the method, strontium was complexed with 4′,4″(5″)‐di‐(tert‐butylcyclohexano)‐18‐crown‐6 in the presence of tetraphenylborate as the counter anion, which increased the hydrophobicity of the ion‐association complex, resulting in its improved extraction into 1‐octanol. Strontium from the organic phase was stripped with nitric acid back to aqueous solution and determined by ion chromatography. The optimum microextraction conditions were as follows: 2.0 mL aqueous samples with 3 mM tetraphenylborate; 150 μL of 1‐octanol as the extractant phase with 10 mM DtBuCH18C6; vortex extraction time for 10 s; centrifugation at 6000 rpm for 4 min; stripping by 0.1 M nitric acid. Under the optimum conditions, the detection limit for strontium was 0.005 mg/L. The calibration curves showed good linearity over the range between 0.01 and 2.5 mg/L. Intra‐ and interday precisions of the present method were satisfactory with relative standard deviations of 1.7 and 2.1%, respectively.     

Vortex‐assisted liquid–liquid microextraction for the rapid screening of short‐chain chlorinated paraffins in water

The rapid screening of trace levels of short‐chain chlorinated paraffins in various aqueous samples was performed by a simple and reliable procedure based on vortex‐assisted liquid–liquid microextraction combined with gas chromatography and electron capture negative ionization mass spectrometry. The optimal vortex‐assisted liquid–liquid microextraction conditions for 20 mL water sample were as follows: extractant 400 μL of dichloromethane; vortex extraction time of 1 min at 2500 × g; centrifugation of 3 min at 5000 × g; and no ionic strength adjustment. Under the optimum conditions, the limit of quantitation was 0.05 μg/L. Precision, as indicated by relative standard deviations, was less than 9% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was above 91%. The vortex‐assisted liquid–liquid microextraction with gas chromatography and electron capture negative ionization mass spectrometry method was successfully applied to quantitatively extract short‐chain chlorinated paraffins from samples of river water and the effluent of a wastewater treatment plant, and the concentrations ranged from 0.8 to 1.6 μg/L.     

Fast screening of aflatoxins in dairy cattle feeds with CE‐LIF method combined with preconcentration technique of vortex assisted low density solvent–microextraction

Aflatoxin contamination in agricultural products poses a great threat to humans and livestock. The aim of this study was to establish a simple, rapid, highly sensitive, and inexpensive method for the simultaneous detection of aflatoxin B₁, B₂, G₁, and G₂ in agricultural products. We used a vortex assisted low density solvent–microextraction (VALDS‐ME) technique for sample preconcentration and sample detection was achieved with a CE‐LIF method. Aflatoxins were separated in an uncoated fused‐silica capillary with the MEKC mode and were excited by a 355 nm UV laser to produce native fluorescence for detection. The obtained LOD and LOQ for the four aflatoxins were in the range of 0.002–0.075 and 0.007–0.300 μg/L, respectively, and the analysis time was within 6.5 min. Using the established method, aflatoxins were screened in naturally contaminated dairy cattle feed samples including alfalfa, bran, and corn kernel. The result shows that the alfalfa and bran samples were contaminated with aflatoxins to varying degrees. Compared with other analytical techniques for aflatoxin screening in agricultural products, this CE‐LIF method combined with VALDS‐ME preconcentration technique is simple, rapid, highly efficient, and inexpensive.     

Optimized determination of polybrominated diphenyl ethers by ultrasound‐assisted liquid–liquid extraction and high‐performance liquid chromatography

A method based on ultrasound‐assisted liquid–liquid extraction and high‐performance liquid chromatography has been optimized for the determination of six polybrominated diphenyl ether congeners. The optimal condition relevant to the extraction was first investigated, more than 98.7 ± 0.7% recovery was achieved with dichloromethane as extractant, 5 min extraction time, and three cycles of ultrasound‐assisted liquid–liquid extraction. Then multiple function was employed to optimize polybrominated diphenyl ether detection conditions with overall resolution and chromatography signal area as the responses. The condition chosen in this experiment was methanol/water 93:7 v/v, flow rate 0.80 mL/min, column temperature 30.0°C. The optimized technique revealed good linearity (R² > 0.9962 over a concentration range of 1–100 μg/L) and repeatability (relative standard deviation < 6.3%). Furthermore, the detection limit (S/N = 3) of the method were ranged from 0.02 to 0.13 μg/L and the quantification limit (S/N = 10) ranged from 0.07 to 0.35 μg/L. Finally, the proposed method was applied to spiked samples and satisfactory results were achieved. These results indicate that ultrasound‐assisted liquid–liquid extraction coupled with high‐performance liquid chromatography was effective to identify and quantify the complex polybrominated diphenyl ethers in effluent samples.     

Reversed‐phase vortex‐assisted liquid–liquid microextraction: A new sample preparation method for the determination of amygdalin in oil and kernel samples

A novel, simple, and rapid reversed‐phase vortex‐assisted liquid–liquid microextraction coupled with high‐performance liquid chromatography has been introduced for the extraction, clean‐up, and preconcentration of amygdalin in oil and kernel samples. In this technique, deionized water was used as the extracting solvent. Unlike the reversed‐phase dispersive liquid–liquid microextraction, dispersive solvent was eliminated in the proposed method. Various parameters that affected the extraction efficiency, such as extracting solvent volume and its pH, vortex, and centrifuging times were evaluated and optimized. The calibration curve shows good linearity (r² = 0.9955) and precision (RSD < 5.2%) in the range of 0.07–20 μg/mL. The limit of detection and limit of quantitation were 0.02 and 0.07 μg/mL, respectively. The recoveries were in the range of 96.0–102.0% with relative standard deviation values ranging from 4.0 to 5.1%. Unlike the conventional extraction methods for plant extracts, no evaporative and re‐solubilizing operations were needed in the proposed technique.     

Determination of zearalenone in maize products by vortex‐assisted ionic‐liquid‐based dispersive liquid–liquid microextraction with high‐performance liquid chromatography

A novel method has been developed for the analysis of zearalenone in maize products by vortex‐assisted ionic‐liquid‐based dispersive liquid–liquid microextraction combined with HPLC and fluorescence detection. Maize samples were extracted with methanol/water (80:20, v/v) and the extraction solution was then used as the dispersive solvent in the microextraction procedure. The analyte was rapidly transmitted to a small volume of ionic liquid and was determined by HPLC. Various parameters affecting the recovery of the mycotoxin were investigated, such as the type and volume of the extraction solvent, the type and volume of the dispersive solvent, the pH of the aqueous phase, the salt addition, and the time of vortex and centrifugation. Under the optimal experimental conditions, a good linearity of the analyte was obtained in the range of 1.0–1000.0 μg/L with the correlation coefficient of 0.9998. The limit of detection (S/N = 3) and quantification (S/N = 10) were 0.3 and 1.0 μg/kg, and the mean recoveries ranged from 83.5 to 94.9%, with a relative standard deviation less than 5.0%. The proposed method was demonstrated to be simple, cheap, quick, and highly selective and was successfully applied to the determination of zearalenone in maize products.     

Alternative solvent‐based methyl benzoate vortex‐assisted dispersive liquid–liquid microextraction for the high‐performance liquid chromatographic determination of benzimidazole fungicides in environmental water samples

Vortex‐assisted dispersive liquid–liquid microextraction using methyl benzoate as an alternative extraction solvent for extracting and preconcentrating three benzimidazole fungicides (i.e., carbendazim, thiabendazole, and fluberidazole) in environmental water samples before high‐performance liquid chromatographic analysis has been developed. The selected microextraction conditions were 250 μL of methyl benzoate containing 300 μL of ethanol, 1.0% w/v sodium acetate, and vortex agitation speed of 2100 rpm for 30 s. Under optimum conditions, preconcentration factors were 14.5–39.0 for the target fungicides. Limits of detection were obtained in the range of 0.01–0.05 μg/L. The proposed method was then applied to surface water samples and the recovery evaluations at three spiked concentration levels of 5, 30, and 50 μg/L were obtained in the range of 77.4–110.9% with the relative standard deviation <7.4%. The present method was simple, rapid, low cost, sensitive, environmentally friendly, and suitable for the trace analysis of the studied fungicides in environmental water samples.     

Speciation analysis of mercury in sediments using ionic‐liquid‐based vortex‐assisted liquid–liquid microextraction combined with high‐performance liquid chromatography and cold vapor atomic fluorescence spectrometry

An improved novel method based on ionic liquid vortex‐assisted liquid–liquid microextraction has been developed for the extraction of methylmercury, ethylmercury and inorganic mercury in sediment samples prior to analysis by high‐performance liquid chromatography with cold vapor atomic fluorescence spectrometry. In this work, mercury species were firstly complexed with dithizone, and the complexes were extracted into 1‐hexyl‐3‐methylimidazolium hexafluorophosphate. Key factors that affect the extraction efficiency of mercury species, such as type and amount of ionic liquid and chelatants, extraction time, sample pH, salt effect and matrix effect were investigated. Under the optimum conditions, linearity was found in the concentration range from 0.1–70 ng/g. Limits of detection ranged from 0.037–0.061 ng/g. Reproducibility and recoveries were assessed by extracting a series of six independent sediment samples that were spiked with different concentration levels. Finally, the proposed method was successfully applied in analysis of real sediment samples. In this work, ionic liquids vortex‐assisted liquid–liquid microextraction was for the first time used for the extraction of mercury species in sediment samples. The proposed method was proved to be much simpler and more rapid, as well as more environmentally friendly and efficient compared with the previous methods.     

Separation of cucurbitane triterpenoids from bitter melon drinks and determination of partition coefficients using vortex‐assisted dispersive liquid‐phase microextraction followed by UHPLC analysis

A rapid, effective method applying vortex‐assisted liquid–liquid microextraction before ultra‐high performance liquid chromatography with mass spectrometry and evaporative light scattering detection was developed for the analysis of four cucurbitane triterpenoids (momordicoside L, momordicoside K, momordicoside F₂, and 3β,7β,25‐trihydroxy cucurbita‐5,23(E )‐dien‐19‐al) in bitter melon juices. Variables affecting the extraction efficiency including different extraction solvents, volume of extraction solvent, salt amount, acid condition, vortex speed and time were optimized thoroughly. Under the optimum conditions, precision was determined by the intra‐ and inter‐day tests in a range of 1.1–5.7% and 2.9–4.0% (RSD), respectively, with recoveries between 95.7 and 106.1%. The calibration curves showed good linearity with square correlation coefficient of 0.9936–0.9991 (evaporative light scattering detection) and 0.9858–0.9989 (MS). The detection limits ranged from 0.8–1.9 ng/mL (MS) to 3–10 ng/mL (evaporative light scattering detection) for these compounds. Enrichment factors of four target compounds were between 27 and 63 times. The proposed method was also used to determine the apparent solvent/water partition coefficients of analytes within the range of 53–120. The developed method can effectively enrich and quantify cucurbitane triterpenoids from bitter melon drinks.     

Vortex‐assisted liquid–liquid microextraction using a low‐toxicity solvent for the determination of five organophosphorus pesticides in water samples by high‐performance liquid chromatography

Vortex‐assisted liquid–liquid microextraction followed by high‐performance liquid chromatography with UV detection was applied to determine Isocarbophos, Parathion‐methyl, Triazophos, Phoxim and Chlorpyrifos‐methyl in water samples. 1‐Bromobutane was used as the extraction solvent, which has a higher density than water and low toxicity. Centrifugation and disperser solvent were not required in this microextraction procedure. The optimum extraction conditions for 15 mL water sample were: pH of the sample solution, 5; volume of the extraction solvent, 80 μL; vortex time, 2 min; salt addition, 0.5 g. Under the optimum conditions, enrichment factors ranging from 196 to 237 and limits of detection below 0.38 μg/L were obtained for the determination of target pesticides in water. Good linearities (r > 0.9992) were obtained within the range of 1–500 μg/L for all the compounds. The relative standard deviations were in the range of 1.62–2.86% and the recoveries of spiked samples ranged from 89.80 to 104.20%. The whole proposed methodology is simple, rapid, sensitive and environmentally friendly for determining traces of organophosphorus pesticides in the water samples.     

Salt‐assisted liquid–liquid extraction in microchannel

In this study, for the first time, salt‐assisted liquid–liquid extraction was performed in a microchannel system. The proposed design is based on the increase of contact surface area between target analytes and extracting phase during the sample and extracting phase transfer in microchannel. In this method, first sample solution, extracting solvent, and salt were mixed by stirrer and simultaneously delivered into a microchannel using a syringe pump. In order to optimize the influential parameters on the extraction efficiency of the proposed method, zidovudine and tenofovir disoproxil fumarate were selected as model analytes. The main parameters such as extracting solvent and its volume, salt amount, pH of sample solution, and microchannel shape, length, and its inner diameter were investigated and optimized. Under the optimized conditions, the proposed method was linear in the range of 0.1–30 µg/mL and R² coefficients were equal to 0.9922 and 0.9947 for zidovudine and tenofovir disoproxil fumarate, respectively. Extraction efficiency of the proposed method was compared with conventional salt‐assisted liquid–liquid extraction. The results show that the proposed design has higher extraction efficiency than conventional salt‐assisted liquid–liquid extraction. Finally, the proposed method was successfully applied for the determination of zidovudine and tenofovir disoproxil fumarate in plasma samples.     

Application of an optimized dispersive nanomaterial ultrasound‐assisted microextraction method for preconcentration of carbofuran and propoxur and their determination by high‐performance liquid chromatography with UV detection

An extraction method based on dispersive nanomaterial ultrasound‐assisted microextraction was used for the preconcentration of carbofuran and propoxur insecticides in water samples prior to high‐performance liquid chromatography with UV detection. ZnS:Ni nanoparticles were synthesized based on the reaction of the mixture of zinc acetate and nickel acetate with thioacetamide in aqueous media and then loaded on activated carbon (ZnS:Ni‐AC). Different methods were used for recognizing the properties of ZnS:Ni‐AC and then this nanomaterial was used for extraction of carbamate insecticide as new adsorbent. The influence of variables on the extraction method (such as amount of adsorbent (mg: NiZnS‐AC), pH and ionic strength of sample solution, vortex and ultrasonic time (min), ultrasound temperature and desorption volume (mL) was investigated by a screening 2^7–4 Plackett–Burman design. Then the significant variables were optimized by using a central composite design combined with a desirability function. At optimum conditions, this method had linear response >0.0060–10 μg/mL with detection limit 0.0015 μg/mL and relative standard deviations <5.0% (n = 3).     

Determination of metal ions in tea samples using task‐specific ionic liquid‐based ultrasound‐assisted dispersive liquid–liquid microextraction coupled to liquid chromatography with ultraviolet detection

Task‐specific ionic liquid‐based ultrasound‐assisted dispersive liquid–liquid microextraction was used for the preconcentration of cadmium(II), cobalt(II), and lead(II) ions in tea samples, which were subsequently analyzed by liquid chromatography with UV detection. The proposed method of preconcentration is free of volatile organic compounds, which are often used as extractants and dispersing solvents in classic techniques of microextraction. A task‐specific ionic liquid trioctylmethylammonium thiosalicylate was used as an extractant and a chelating agent. Ultrasound was used to disperse the ionic liquid. After microextraction, the phases were separated by centrifugation, and the ionic liquid phase was solubilized in methanol and directly injected into the liquid chromatograph. Selected microextraction parameters, such as the volume of ionic liquid, the pH of the sample, the duration of ultrasound treatment, the speed and time of centrifugation, and the effect of ionic strength, were optimized. Under optimal conditions an enrichment factor of 200 was obtained for each analyte. The limits of detection were 0.002 mg/kg for Cd(II), 0.009 mg/kg for Co(II), and 0.013 mg/kg for Pb(II). The accuracy of the proposed method was evaluated by an analysis of the Certified Reference Materials (INCT‐TL‐1, INCT‐MPH‐2) with the recovery values in the range of 90–104%.     

Ultrasound‐assisted temperature‐controlled ionic liquid emulsification microextraction coupled with capillary electrophoresis for the determination of parabens in personal care products

We developed a CE and ultrasound‐assisted temperature‐controlled ionic liquid emulsification microextraction method for the determination of four parabens (methyl paraben, ethyl paraben, propyl paraben, and butyl paraben) in personal care products including mouthwash and toning lotion. In the proposed extraction procedure, ionic liquid (IL, 1‐octyl‐3‐methylimidazolium hexafluorophosphate) was used as extraction solvent, moreover, no disperser solvent was needed. Parameters affecting the extraction efficiency including volume of IL, heating temperature, ultrasonic time, extraction time, sample pH, ionic strength, and centrifugation time were optimized. Under the optimized conditions, the method was found to be linear over the range of 3–500 ng/mL with coefficient of determination (R²) in the range of 0.9990–0.9998. The LODs and LOQs for the four parabens were 0.45–0.72 ng/mL and 1.50–2.40 ng/mL, respectively. Intraday and interday precisions (RSDs, n = 5) were in the range of 5.4–6.8% and 7.0–8.7%, respectively. The recoveries of parabens at different spiked levels ranged from 71.9 to 119.2% with RSDs less than 9.5%.     

Simultaneous determination of furfural and its degradation products,furoic acid and maleic acid,in transformer oil by the reversed‐phase vortex‐assisted liquid–liquid microextraction followed by high‐performance liquid chromatography

To explore why the use of furfural as a transformer oil‐paper insulation aging characteristic is problematic in real world application, we developed a method for the simultaneous determination of furfural, furoic acid, and maleic acid in transformer oil by reversed‐phase vortex‐assisted liquid–liquid microextraction combined with high‐performance liquid chromatography. The conditions for the proposed method were optimized, and the obtained extract can be directly analyzed by high‐performance liquid chromatography. The detection limits (signal‐to‐noise ratio = 3) of the method ranged from 1.0 to 4.6 μg/L, the enrichment factors for furfural, furoic acid, maleic acid, and fumaric acid were 4.6, 25.1, 15.6, and 17.5, respectively, and the recovery rates for three analytes (fumaric acid was undetected) range from 82.1 to 106.2%. The contents of furfural, furoic acid, and maleic acid resulted from accelerated aging of transformer insulation oil‐paper were measured using the present method for the first time, and the aging samples were analyzed by liquid chromatography with mass spectrometry for the identification of furoic acid and maleic acid in the aging transformer oil samples. Using the optimal method, the target products of samples at different aging time were tracked and measured.     

Determination of phthalate esters in liquor samples by vortex‐assisted surfactant‐enhanced‐emulsification liquid–liquid microextraction followed by GC–MS

A novel method using vortex‐assisted surfactant‐enhanced‐emulsification liquid–liquid microextraction has been developed for the extraction of phthalate esters (PAEs) in Chinese liquor samples prior to analysis by GC–MS. In the proposed method, a high‐density extraction solvent (carbon tetrachloride) was dispersed into samples with the aid of a surfactant (Triton X‐100) and vortex agitation, resulting in a short extraction equilibrium (30 s). After centrifugation, a single microdrop of solvent was easily collected for GC–MS analysis. Key factors that affected the extraction efficiency were optimized. Under the optimum conditions, linearity was found in the range from 0.05 to 50 μg/L. Coefficients of determination varied from 0.9938 to 0.9971. LODs, based on an S/N of 3, ranged from 4.9 to 13 ng/L. Enrichment factors varied from 140 to 184. Reproducibility and recoveries were assessed by testing a series of three liquor samples that were spiked with different concentration levels. Finally, the proposed method was successfully applied to the determination of PAEs in 16 Chinese liquor samples. In this work, high‐density‐solvent vortex‐assisted surfactant‐enhanced‐emulsification liquid–liquid microextraction was applied for the first time for the extraction of PAEs in Chinese liquor samples and was proved to be simple, rapid, and sensitive.