Fluidized-bed extraction of polycyclic aromatic hydrocarbons from contaminated soil samples

Summary Due to the carcinogenity and ubiquity of polycyclic aromatic hydrocarbons in the environment they are of ongoing interest to analytical chemistry. In this study, a comparison of the classic Soxhlet extraction and, fluidized-bed extraction, has been conducted. The extraction of polycyclic aromatic hydrocarbons by this technique has been optimized considering as experimental variables the variation of the number of extraction cycles and the holding time after reaching the heating temperature by means of a surface response design. The significance of the operational parameters of the fluidized-bed extraction on the performance characteristics has been investigated. For the determination of the analytes a selective clean-up of the extracts followed by a fast gas chromatography method with mass spectrometric detection was used, resulting in low limits of detection (0.2 pg μL⁻¹). The accuracy of the complete analytical method was established by extraction and analysis of reference materials.     

Optimisation of supercritical fluid extraction of polycyclic aromatic hydrocarbons and their nitrated derivatives adsorbed on highly sorptive diesel particulate matter

Supercritical fluid extraction (SFE) was performed to extract complex mixtures of polycyclic aromatic hydrocarbons (PAHs), nitrated derivatives (nitroPAHs) and heavy n-alkanes from spiked soot particulates that resulted from the incomplete combustion of diesel oils. This polluted material, resulting from combustion in a light diesel engine and collected at high temperature inside the particulate filter placed just after the engine, was particularly resistant to conventional extraction techniques, such as soxhlet extraction, and had an extraction behaviour that differed markedly from certified reference materials (SRM 1650). A factorial experimental design was performed, simultaneously modelling the influence of four SFE experimental factors on the recovery yields, i.e.: the temperature and the pressure of the supercritical fluid, the nature and the percentage of the organic modifier added to CO₂ (chloroform, tetrahydrofuran, methylene chloride), as a means to reach the optimal extraction yields for all the studied target pollutants. The results of modelling showed that the supercritical fluid pressure had to be kept at its maximum level (30 MPa) and the temperature had to be kept relatively low (75 °C). Under these operating conditions, adding 15% of methylene chloride to the CO₂ permitted quantitative extraction of not only light PAHs and their nitrated derivatives, but also heavy n-alkanes from the spiked soots. However, heavy polyaromatics were not quantitatively extracted from the refractory carbonaceous solid surface. As such, original organic modifiers were tested, including pyridine, which, as a strong electron donor cosolvent (15% into CO₂), was the most successful. The addition of diethylamine to pyridine, which enhanced the electron donor character of the cosolvent, even increased the extraction yields of the heaviest PAHs, leading to a quantitative extraction of all PAHs (more than 79%) from the diesel particulate matter, with detection limits ranging from 0.5 to 7.8 ng for 100 mg of spiked material. Concerning the nitrated PAHs, a small addition of acetic acid into pyridine, as cosolvents, gave the best results, leading to fair extraction yields (approximately 60%), with detection limits ranging from 18 to 420 ng.     

Gas purge-microsyringe extraction: A rapid and exhaustive direct microextraction technique of polycyclic aromatic hydrocarbons from plants

Gas purge-microsyringe extraction (GP-MSE) is a rapid and exhaustive microextraction technique for volatile and semivolatile compounds. In this study, a theoretical system of GP-MSE was established by directly extracting and analyzing 16 kinds of polycyclic aromatic hydrocarbons (PAHs) from plant samples. On the basis of theoretical consideration, a full factorial experimental design was first used to evaluate the main effects and interactions of the experimental parameters affecting the extraction efficiency. Further experiments were carried out to determine the extraction kinetics and desorption temperature-dependent. The results indicated that three factors, namely desorption temperature (temperature of sample phase) T_d, extraction time t, and gas flow rate u, had a significantly positive effect on the extraction efficiency of GP-MSE for PAHs. Extraction processes of PAHs in plant samples followed by first-order kinetics (relative coefficient R² of simulation curves were 0.731–1.000, with an average of 0.958 and 4.06% relative standard deviation), and obviously depended on the desorption temperature. Furthermore, the effect of the matrix was determined from the difference in E_app,d. Finally, satisfactory recoveries of 16 PAHs were obtained using optimal parameters. The study demonstrated that GP-MSE could provide a rapid and exhaustive means of direct extraction of PAHs from plant samples. The extraction kinetics were similar that of the inverse process of the desorption kinetics of the sample phase.     

Characterization of polycyclic aromatic hydrocarbons in environmental samples by selective fluorescence quenching

Selective fluorescence quenching is used to profile polycyclic aromatic hydrocarbons (PAHs) in samples of environmental origin. After separation by high-efficiency capillary liquid chromatography, the PAHs are detected by laser-induced fluorescence spectroscopy. Nitromethane is added to selectively quench the fluorescence of alternant PAHs, whereas diisopropylamine is added to quench nonalternant PAHs. The chromatograms in the absence and presence of fluorescence quenching are evaluated by means of the product moment correlation method to quantify the statistical similarities and differences. This method is demonstrated by application to three samples: a standard mixture of 16 priority pollutants, a coal-derived fluid, and a contaminated soil. The correlation coefficients (r) are typically 0.99 or higher for samples that are identical in origin, 0.90-0.50 for closely related samples, and less than 0.50 for samples that are distinctly unrelated. This method can be used to confirm with high statistical confidence the cause or source of an event with environmental impact, such as an oil leak or spill, contamination or waste by-products from petroleum fuel production and processing, etc.     

Water stability of zeolite imidazolate framework 8 and application to porous membrane-protected micro-solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples

Zeolite imidazolate framework 8 (ZIF-8) has permanent porosity, high surface area, hydrophobic property, open metal sites and remarkable water stability. These novel properties characterize the material as being different from other moisture sensitive metal-organic frameworks and endow ZIF-8 with the potential to extract trace analytes from environmental water samples. In the present study, ZIF-8 was synthesized and used as a sorbent for micro-solid-phase extraction of 6 polycyclic aromatic hydrocarbons (PAHs) from environmental water samples for the first time. Parameters influencing the extraction efficiency such as desorption time, extraction time, desorption solvent and salt concentration were investigated. Environmental water samples collected from a local lake were processed using this novel μ-SPE procedure. ZIF-8 proved to be a very efficient extraction sorbent for the extraction of trace analytes from water samples. The limits of detection from gas chromatography-mass spectrometric analysis of PAHs were 0.002-0.012 ng/ml. The linear ranges were 0.1-50 or 0.5-50 ng/ml. The relative standard deviations for five replicates of the extractions were in the range of 2.1-8.5%.     

Pressurised liquid extraction of polycyclic aromatic hydrocarbons from gas and particulate phases of atmospheric samples

Pressurised liquid extraction (PLE) was applied to determine the atmospheric levels of 16 polycyclic aromatic hydrocarbons (PAHs) in the gas and particulate phases. The method involved high‐volume air sampling with quartz fibre filters (QFFs) and polyurethane foam (PUF) plugs and analytes were subsequently extracted from the samples by PLE, and determined with GC‐MS. We optimised the PLE conditions for the solvent, the number of cycles and extraction temperature. Recoveries were higher than 90% for most compounds. Method LODs and LOQs were between 0.001 and 0.02 ng/m³ and between 0.01 and 0.05 ng/m³. Air samples were taken from a site in the region of Tarragona in Catalonia, Spain, where one of the largest petrochemical complexes in southern Europe is located. The total concentration of PAHs were from 6.7 to 27.66 ng/m³, with predominant levels of PAHs appearing in the gas phase (48–81%), and an average level of benzo[a]pyrene, the most carcinogenic PAH, of 0.86 ng/m³.     

Extraction of polycyclic aromatic hydrocarbons and organochlorine pesticides from soils: a comparison between Soxhlet extraction, microwave-assisted extraction and accelerated solvent extraction techniques

The methods of simultaneous extraction of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) from soils using Soxhlet extraction, microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) were established, and the extraction efficiencies using the three methods were systemically compared from procedural blank, limits of detection and quantification, method recovery and reproducibility, method chromatogram and other factors. In addition, soils with different total organic carbon contents were used to test the extraction efficiencies of the three methods. The results showed that the values obtained in this study were comparable with the values reported by other studies. In some respects such as method recovery and reproducibility, there were no significant differences among the three methods for the extraction of PAHs and OCPs. In some respects such as procedural blank and limits of detection and quantification, there were significant differences among the three methods. Overall, ASE had the best extraction efficiency compared to MAE and Soxhlet extraction, and the extraction efficiencies of MAE and Soxhlet extraction were comparable to each other depending on the property such as TOC content of the studied soil. Considering other factors such as solvent consumption and extraction time, ASE and MAE are preferable to Soxhlet extraction.     

Optimisation of the extraction of polycyclic aromatic hydrocarbons and their nitrated derivatives from diesel particulate matter using microwave-assisted extraction

Pressurised microwave-assisted extraction was used to extract a complex mixture containing polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs and heavy n-alkanes from a particularly refractory carbonaceous material resulting from the combustion in a diesel engine. A second-order central composite design was used to determine the optimal conditions of extraction in terms of time, temperature, volume and nature of extracting solvent from spiked diesel soots. To begin, methylene chloride, tetrahydrofuran and chloroform were tested for extracting the spiked diesel particulates; however, the nature of these solvents was not really an influential factor. Volume was the most influential factor and was kept at a medium level to enhance the extraction of heavy PAHs without introducing an important dilution factor. Temperature and time were not influential as main factors but interacted with the other factors. Finally, high temperature and duration associated with a medium volume of methylene chloride were better for the extractions. After this optimisation, five-ring and six-ring PAHs were nevertheless not satisfactorily desorbed. Other solvents were therefore tested. Only aromatic ones, and particularly heterocyclic aromatic solvents, managed to desorb the heaviest PAHs. Pyridine, with its both aromatic and its basic character, was the most successful solvent. Desorption was even complete with an addition of 17% of diethylamine into pyridine. So, using MAE, we succeeded in extracting quantitatively, from the spiked refractory diesel soot surface, two-ring to six-ring PAHs, heavy n-alkanes and short nitrated PAHs. However, heavy nitrated PAHs were better extracted with a small addition of acetic acid (1%) into pyridine instead of a basic cosolvent.     

Development of multiwalled carbon nanotubes based micro-solid-phase extraction for the determination of trace levels of sixteen polycyclic aromatic hydrocarbons in environmental water samples

Micro-solid-phase extraction (μ-SPE) was developed for the determination of trace level of 16 United States Environmental Protection Agency priority polycyclic aromatic hydrocarbons (PAHs) in river water samples with gas chromatography-mass spectrometry (GC-MS). In the μ-SPE device, multiwalled carbon nanotubes was employed as sorbent and was packed inside an porous polypropylene membrane "envelope" whose edges were heat-sealed to secure the contents. The μ-SPE device was placed in a stirred sample solution to extract the analytes. The porous polypropylene membrane envelope in μ-SPE device acts as a filter to exclude potential interferences, such as eliminating or reducing the influence of particles that are bigger than the pore size. After extraction, analyte desorption was carried out with a suitable organic solvent under ultrasonication. Important extraction parameters were optimized in detail, including the selection and amount of sorbent materials, the extraction temperature and extraction time, desorption solvent and desorption time, amount of organic modifier, agitation speed and sample ionic strength. Under the developed extraction conditions, the proposed method provided good linearity in the range of 0.1-50 μg/L, low limits of detection (4.2-46.5 ng/L), and good repeatability of the extractions (relative standard deviations, <12%, n=5). The developed μ-SPE method was successfully applied to the extraction of PAHs in river water samples. The μ-SPE method was demonstrated to be a fast and efficient method for the determination of PAHs from environmental water samples.     

Determination of polycyclic aromatic hydrocarbons in waters by ultrasound-assisted emulsification-microextraction and gas chromatography-mass spectrometry

An ultrasound-assisted emulsification-microextraction (USAEME) procedure was developed for the extraction of US EPA 16 polycyclic aromatic hydrocarbons (PAHs) in 10 mL of water samples, with subsequent determination by gas chromatography-mass spectrometry (GC-MS). After determination of the most suitable solvent and solvent volume, several other parameters (i.e., extraction time, centrifugation time and ionic strength of the sample) were optimized using a 2³ factorial experimental design. Limits of detection ranged from 0.001 to 0.036 μg L⁻¹. The developed procedure was applied to fortified distilled water with different fortification levels (0.5, 2 and 5 μg L⁻¹). Recoveries were over 92% and relative standard deviations of the recoveries were below 8%. The efficiency of the USAEME was compared with traditional liquid-liquid extraction (LLE) and solid-phase extraction on real water samples (i.e., tap water, well water and surface (lake) water as well as domestic and industrial wastewaters). The USAEME showed comparable efficiencies especially with LLE. The developed USAEME was demonstrated to be robust, viable, simple, rapid and easy to use for the determination of PAHs in water samples by GC-MS.     

Evaluation of metal‐organic framework 5 as a new SPE material for the determination of polycyclic aromatic hydrocarbons in environmental waters

Metal‐organic frameworks, a new class of materials with high surface area and great porosity, have been widely applied in gas sorption. It is generally known that metal‐organic framework 5 cannot be applied in aqueous phase since it is water sensitive. However, this work reveals that the derived material of metal‐organic framework 5 is a good SPE sorbent that can be applied to aqueous phases. Metal‐organic framework 5 was prepared and used as a SPE sorbent for the determination of polycyclic aromatic hydrocarbons in environmental matrices coupling with HPLC. The water treatment induced changes in the properties were investigated in detail. Even though metal‐organic framework 5 is conversed to a second phase after water treatment, it still shows high extraction ability. Under the optimized experimental conditions, good sensitivity levels were achieved with low LODs ranging from 0.4 to 4.0 ng L^?1 and a linearity of 0.004–20 μg L^?1 (R² > 0.996) for the investigated polycyclic aromatic hydrocarbons. The method has been validated in the analysis of real water samples with recoveries in the range of 80.2–120.2% and RSDs in the range of 0.5–11.7%.     

Extraction of polycyclic aromatic hydrocarbons from smoked fish using pressurized liquid extraction with integrated fat removal

Quantification of polycyclic aromatic hydrocarbons (PAHs) in smoked fish products often requires multiple clean-up steps to remove fat and other compounds that may interfere with the chemical analysis. We present a novel pressurized liquid extraction (PLE) method that integrates exhaustive extraction with fat retention in one single analytical step. The PLE parameters: type of fat retainer, flush volume, solvent composition, fat-to-fat retainer ratio (FFR), and the dimensions of the extraction cells were the most important factors for obtaining fat-free extracts with high recoveries of PAHs. A 100 mL extraction cell filled with 18 g activated silica gel, dichloromethane:hexane (15:85, v/v) as extraction solvent, FFR of 0.025 and 100% flush volume was the best analytical setup for integrated extraction and fat retention.The one-step procedure provided a more rapid and cost-efficient alternative with minimization of waste generation compared to the standard reference method that is based on a multi-step procedure. Furthermore, the analytical quality of the two methods are comparable, while the new integrated approach for extraction and cleanup is less prone to analytical errors (random and systematic) because of fewer analytical steps.     

[Hmim]PF6 enhanced the extraction of polycyclic aromatic hydrocarbons from soil with the QuEChERS method

To detect, identify, and quantify the polycyclic aromatic hydrocarbons (PAHs) released into the environment, the PAHs need to be isolated from the soil matrix. In this work, a modified quick, easy, cheap, efficient, rugged and safe (QuEChERS) method with ionic liquid was combined with liquid chromatography to identify 16 selected PAHs in soil. Ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim]PF₆) was applied as an extractant component to enhance the process. The [Hmim]PF₆ content in acetonitrile (ACN) was optimized. The [Hmim]PF₆ modified QuEChERS method has the advantages defined by its name and a similar recovery to other extraction methods reported in the literature. Adding [Hmim]PF₆ may eliminate the co-extract proportion and achieve a more effective extraction. Compared with ACN alone, the matrix effect (ME) of ACN containing 5% [Hmim]PF₆ was reduced by approximately 35%. Additionally, the ME of using ACN containing [Hmim]PF₆ without a clean-up procedure was similar to that of using ACN followed by a clean-up procedure. The recoveries of the QuEChERS method implemented with [Hmim]PF₆ ranged from 75.19% to 100.98%. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.86 to 4.51 µg/kg and from 2.87 to 15.13 µg/kg, respectively.     

Magnetic N-doped carbon nanotubes: A versatile and efficient material for the determination of polycyclic aromatic hydrocarbons in environmental water samples

This paper describes a new, efficient and versatile method for the sampling and preconcentration of PAH in environmental water matrices using special hybrid magnetic carbon nanotubes. These N-doped amphiphilic CNT can be easily dispersed in any aqueous matrix due to the N containing hydrophilic part and at the same time show high efficiency for the adsorption of different PAH contaminants due to the very hydrophobic surface. After adsorption, the CNT can be easily removed from the medium by a simple magnetic separation. GC/MS analyses showed that the CNT method is more efficient than the use of polydimethylsiloxane (PDMS) with much lower solvent consumption, technical simplicity and time, showing good linearity (range 0.18–80.00 μg L⁻¹) and determination coefficient (R² > 0.9810). The limit of detection ranged from 0.05 to 0.42 μg L⁻¹ with limit of quantification from 0.18 to 1.40 μg L⁻¹. Recovery (n = 9) ranged from 80.50 ± 10 to 105.40 ± 12%. Intraday precision (RSD, n = 9) ranged from 1.91 to 9.01%, whereas inter day precision (RSD, n = 9) ranged from 7.02 to 17.94%. The method was applied to the analyses of PAH in four lake water samples collected in Belo Horizonte City, Brazil.     

Development of a focused ultrasonic-assisted extraction of polycyclic aromatic hydrocarbons in marine sediment and mussel samples

Focused ultrasonic-assisted extraction (FUSE) is a new and particular technique based on the cavitation effect. In this work, the focused ultrasound assisted extraction was studied and developed for the extraction of polycyclic aromatic hydrocarbons from marine sediments and mussel tissues. The variables influencing the extraction (amplitude of the ultrasound pulse, the extraction time and the solvent) were studied by a full factorial design and a central composite design. As a result, flat response surfaces were obtained and the most convenient conditions were 45% of ultrasound amplitude, 120 s of extraction time and 5 mL of acetone. Both accuracy and precision of the method were evaluated by means of two certified reference materials (marine sediment and mussel tissue) and the results were also compared to those obtained by microwave assisted extraction.     

Room-temperature fluorescence spectroscopy of monohydroxy metabolites of polycyclic aromatic hydrocarbons on octadecyl extraction membranes

Urine analysis of monohydroxy metabolites is recognized as an accurate assessment of human exposure to polycyclic aromatic hydrocarbons. Despite the sophisticated arsenal of analytical tools, monitoring of monohydroxy metabolites via simple, cost effective and direct methods of analysis still remains a challenge. This article evaluates the analytical potential of solid-phase extraction room-temperature fluorescence spectroscopy for the problem at hand. Extraction membranes serve the dual purpose of sample pre-concentration and solid substrate for RTF measurements. The potential of our proposition is demonstrated with the analysis of 2-hydroxy-fluorene, 1-hydroxy-pyrene, 3-hydroxy-benzo[a]pyrene and 9-hydroxy-phenanthrene in synthetic urine samples. Signal reproducibility is improved with the aid of a sample holder specifically designed for the manual optimization of luminescence signals. Background correction of solid substrates is carried out with the aid of Asymmetric Least Squares. Recovery values for the studied metabolites varied from 99.0 ± 1.2% (3-hydroxy-benzo[a]pyrene) to 99.9 ± 0.05% (1-hydroxy-pyrene). With only 10 mL of urine sample, the limits of detection varied from 57 pg mL⁻¹ (2-hydroxy-fluorene) to 2 pg mL⁻¹ (1-hydroxy-pyrene). Additional figures of merit include a simple experimental procedure for routine screening of numerous samples and compatibility with portable instrumentation for field analysis. Because of the non-destructive nature of fluorescence measurements, membranes can be brought to the lab for subsequent elution and confirmation of compounds via high-resolution techniques.     

Comparative performance of extraction strategies for polycyclic aromatic hydrocarbons in peats

The assessment of historical trends in atmospheric deposition of organic contaminants by using peat samples has been reported on several occasions because these samples represent an almost ideal medium for recording temporal changes in organic contaminant deposition rates. The determination of polycyclic aromatic hydrocarbons (PAHs) in peat samples is complicated due to the high content of organic matter in peat, which affects both extraction efficiency and analytical quality. A rapid and simple method is proposed for the determination of 10 US Environmental Protection Agency indicator PAHs in complex matrices such as peat. This article reviews and addresses the most relevant analytical methods for determining PAHs in peat. We discuss and critically evaluate three different extraction procedures, such as ultrasound-assisted solvent extraction (UASE), shaking and pressurized liquid extraction (PLE). Clean-up of extracts was performed by solid-phase extraction using silica cartridges. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted, concluding that the UASE extraction method using hexane:dichloromethane (80:20) as extractant was robust enough to determine the selected PAHs in peat samples with estimated quantification limits between 0.050 and 3.5 μg/kg depending on the PAH. UASE did not demand sophisticated equipment and long extraction times. PLE involved sophisticated equipment and showed important variations in the results. The method proposed was applied to the determination of PAHs in peat samples from Xistral Mountains (Galicia, Spain).     

Ultrasound-assisted extraction of nitropolycyclic aromatic hydrocarbons from soil prior to gas chromatography-mass detection

Continuous ultrasound-assisted extraction of nitropolycyclic aromatic hydrocarbons from soil prior to their individual separation and determination by gas chromatography (GC) with MS-MS detection is presented here. A multivariate optimisation of the variables affecting the continuous extraction step (namely, probe position, ultrasound radiation amplitude, percentage of duty cycle of ultrasonic exposure, sonication time, total extractant volume, extractant flow rate and temperature of the water-bath in which the extraction cell was placed) was performed. The method was compared with the reference EPA method 3540 using natural contaminated soils. Similar efficiencies were obtained but with a drastic reduction of both the extraction time (10 min versus 24 h) and the extractant volume (less than 10 ml versus 100 ml) by the proposed method. Detection limits of low picogram were obtained, with repeatability and reproducibility between 4.21-5.70 and 5.20-7.23%, respectively.     

Assaying particle-bound polycyclic aromatic hydrocarbons from archived PM2.5 filters

Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect both gas-phase and particle-phase PAH constituents. Here, we report an assay for measuring particle-bound PAHs in archived filters from the network of U.S. monitoring stations for particles less than 2.5 microm in diameter (PM2.5), without the need for deploying specialized samplers. PAHs are extracted from Teflon filters with dichloromethane, concentrated, and measured at trace levels using gas chromatography-mass spectrometry. Although PAHs with 3-6 aromatic rings can be assayed, results are only unambiguously accurate for compounds with 5- or 6-rings, due to variable vaporization losses of the more volatile 3- and 4-ring compounds during sampling and/or storage. The method was evaluated for sensitivity, recovery, precision, and agreement of paired air samples, using PM2.5 samplers locally in Chapel Hill, NC. Additionally, three sets of archived samples were analyzed from a study of PM2.5 in the Czech Republic. Levels of some 4-ring and all 5- and 6-ring PAHs in both the local and Czech samples were consistent with published results from investigations employing PAH-specific air samplers. This work strongly suggests that assessment of particle-bound 5- and 6-ring PAHs from archived PM2.5 filters is quantitatively robust. The assay may also be useful for selected 4-ring compounds, notably chrysene and benzo(a)anthracene, if PM2.5 filters are stored under refrigeration.     

Polytetrafluoroethylene‐jacketed stirrer modified with graphene oxide and polydopamine for the efficient extraction of polycyclic aromatic hydrocarbons

Steel stirrers jacketed with polytetrafluoroethylene can be regarded as an ideal substrate for stirrer bar sorptive extraction. However, it is still a great challenge to immobilize graphene onto a polytetrafluoroethylene stirrer due to the high chemical resistance of the surface of a polytetrafluoroethylene stirrer. We describe here a method to modify the surface of polytetrafluoroethylene stirrers with graphene. In this work, graphene was used as the sorbent due to its excellent adsorption capability for aromatic compounds, such as polycyclic aromatic compounds. Graphene was successfully immobilized onto polytetrafluoroethylene‐stirrer by a bio‐inspired polydopamine functionalization method. The graphene‐modified polytetrafluoroethylene‐stirrer shows good stability and tolerance to stirring, ultrasonication, strong acidic and basic solutions, and to organic solvents. The multilayer coating was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. After the optimization of some experimental conditions, the graphene‐modified polytetrafluoroethylene stirrer was used for the stirrer bar sorptive extraction of polycyclic aromatic hydrocarbons, in which the binding between the polycyclic aromatic hydrocarbons and the graphene layer was mainly based on π–π stacking and hydrophobic interactions. The graphene‐modified polytetrafluoroethylene‐stirrer‐based stirrer bar sorptive extraction and high‐performance liquid chromatography method was developed for the determination of polycyclic aromatic hydrocarbons with great extraction efficiency, with enrichment factors from 18 to 62. The method has low limits of detection of 1–5 pg/mL, wide linear range (5–100 and 10–200 pg/mL), good linearity (R ≥ 0.9957) and good reproducibility (RSD ≤ 6.45%). The proposed method has been applied to determine polycyclic aromatic hydrocarbons in real dust samples. Good recoveries were obtained, ranging from 88.53 to 109.43%.