Determination of polycyclic aromatic hydrocarbons in water by a novel mesoporous‐coated stainless steel wire microextraction combined with HPLC

A novel mesoporous‐coated stainless steel wire microextraction coupled with the HPLC procedure for quantification of four polycyclic aromatic hydrocarbons in water has been developed, based on the sorption of target analytes on a selectively adsorptive fiber and subsequent desorption of analytes directly into HPLC. Phenyl‐functionalized mesoporous materials (Ph‐SBA‐15) were synthesized and coated on the surfaces of a stainless steel wire. Due to the high porosity and large surface area of the Ph‐SBA‐15, high extraction efficiency is expected. The influence of various parameters on polycyclic aromatic hydrocarbons extraction efficiency were thoroughly studied and optimized (such as the extraction temperature, the extraction time, the desorption time, the stirring rate and the ionic strength of samples). The results showed that each compound for the analysis of real water samples was tested under optimal conditions with the linearity ranging from 1.02×10^?3 to 200 μg/ L and the detection limits were found from 0.32 to 2.44 ng/ L, respectively. The RSD of the new method was smaller than 4.10%.     

Poly(ionic liquids)‐coated stainless‐steel wires packed into a polyether ether ketone tube for in‐tube solid‐phase microextraction

An in‐tube solid‐phase microextraction device was developed by packing poly(ionic liquids)‐coated stainless‐steel wires into a polyether ether ketone tube. An anion‐exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)‐coated stainless‐steel wires were characterized by scanning electron microscopy and energy dispersive X‐ray spectrometry. The extraction device was connected to high‐performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03–20 μg/L, detection limits of 0.010–0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1–118.9%.     

Mesoporous titanium oxide with high‐specific surface area as a coating for in‐tube solid‐phase microextraction combined with high‐performance liquid chromatography for the analysis of polycyclic aromatic hydrocarbons

Stainless‐steel wires coated with mesoporous titanium oxide were placed into a polyether ether ketone tube for in‐tube solid‐phase microextraction, and the coating sorbent was characterized by X‐ray diffraction and scanning electron microscopy. It was combined with high‐performance liquid chromatography to build an online system. Using eight polycyclic aromatic hydrocarbons as the analytes, some conditions including sample flow rate, sample volume, organic solvent content, and desorption time were investigated. Under optimum conditions, an online analysis method was established and provided good linearity (0.03–30 μg/L), low detection limits (0.01–0.10 μg/L), and high enrichment factors (77.6–678). The method was applied to determine target analytes in river water and water sample of coal ash, and the recoveries are in the range of 80.6–106.6 and 80.9–103.5%, respectively. Compared with estrogens and plasticizers, extraction coating shows better extraction efficiency for polycyclic aromatic hydrocarbons.     

Polythiophene/hexagonally ordered silica nanocomposite coating as a solid‐phase microextraction fiber for the determination of polycyclic aromatic hydrocarbons in water

A highly porous fiber coated with polythiophene/hexagonally ordered silica nanocomposite was prepared for solid‐phase microextraction (SPME). The prepared nanomaterial was immobilized onto a stainless‐steel wire for the fabrication of the SPME fiber. Polythiophene/hexagonally ordered silica nanocomposite fibers were used for the extraction of some polycyclic aromatic hydrocarbons from water samples. The extracted analytes were transferred to the injection port of a gas chromatograph using a laboratory‐designed SPME device. The results obtained prove the ability of the polythiophene/hexagonally ordered silica material as a new fiber for the sampling of organic compounds from water samples. This behavior is due most probably to the increased surface area of the polythiophene/hexagonally ordered silica nanocomposite. A one‐at‐a‐time optimization strategy was applied for optimizing the important extraction parameters such as extraction temperature, extraction time, ionic strength, stirring rate, and desorption temperature and time. Under the optimum conditions, the LOD of the proposed method is 0.1–3 pg/mL for analysis of polycyclic aromatic hydrocarbons from aqueous samples, and the calibration graphs were linear in a concentration range of 0.001–20 ng/mL (R² > 0.990) for most of the polycyclic aromatic hydrocarbons. The single fiber repeatability and fiber‐to‐fiber reproducibility were less than 8.6 and 19.1% (n = 5), respectively.     

Carbon nanospheres as solid‐phase microextraction coating for the extraction of polycyclic aromatic hydrocarbons from water and soil samples

A solid‐phase microextraction with carbon nanospheres coated fiber coupled with gas chromatographic detection was established for the determination of eight polycyclic aromatic hydrocarbons (naphthalene, biphenyl, acenaphthene, fluorine, phenanthrene, anthracene, fluoranthene, and pyrene) in water and soil samples. The experimental parameters (extraction temperature, extraction time, stirring rate, headspace volume, salt content, and desorption temperature) which affect the extraction efficiency were studied. Under the optimized conditions, good linearity between the peak areas and the concentrations of the analytes was achieved in the concentration range of 0.5‐300 ng/mL for water samples, and in the concentration range of 6.0‐2700 ng/g for soil samples. The detection limits for the analytes were in the range of 0.12‐0.45 ng/mL for water samples, and in the range of 1.53‐2.70 ng/g for soil samples. The method recoveries of the polycyclic aromatic hydrocarbons for spiked water samples were 80.10‐120.1% with relative standard deviations less than 13.9%. The method recoveries of the analytes for spiked soil samples were 80.40‐119.6% with relative standard deviations less than 14.4%. The fiber was reused over 100 times without a significant loss of extraction efficiency.     

Application of sunflower stalk‐carbon nitride nanosheets as a green sorbent in the solid‐phase extraction of polycyclic aromatic hydrocarbons followed by high‐performance liquid chromatography

A green biocomposite of sunflower stalks and graphitic carbon nitride nanosheets has been applied as a solid‐phase extraction adsorbent for sample preparation of five polycyclic aromatic hydrocarbons in different solutions using high‐performance liquid chromatography with ultraviolet detection. Before the modification, sunflower stalks exhibited relatively low adsorption to the polycyclic aromatic hydrocarbons extraction. The modified sunflower stalks showed increased adsorption to the analytes extraction due to the increase in surface and existence of a π–π interaction between the analytes and graphitic carbon nitride nanosheets on the surface. Under the optimal conditions, the limits of detection and quantification for five polycyclic aromatic hydrocarbons compounds could reach 0.4–32 and 1.2–95 ng/L, respectively. The method accuracy was evaluated using recovery measurements in spiked real samples and good recoveries from 71 to 115% with relative standard deviations of <10% have been achieved. The developed method was successfully applied for polycyclic aromatic hydrocarbons determination in various samples—well water, tap water, soil, vegetable, and barbequed meat (kebab)—with analytes contents ranging from 0.065 to 13.3 μg/L. The prepared green composite as a new sorbent has some advantages including ease of preparation, low cost, and good reusability.     

Inhibiting sorbent stripping by designing a sorbent‐packed porous probe for headspace solid‐phase microextraction

To prevent the stripping of coating sorbents in headspace solid‐phase microextraction, a porous extraction probe with packed sorbent was introduced by using a porous stainless steel needle tube and homemade sol–gel sorbents. The traditional stainless‐steel needle tube was punched by a laser to obtain two rows of holes, which supply a passageway for analyte vapor during extraction and desorption. The sorbent was prepared by a traditional sol–gel method with both poly(ethylene glycol) and hydroxy‐terminated silicone oil as coating ingredients. Eight polycyclic aromatic hydrocarbons and six benzene series compounds were used as illustrative semi‐volatile and volatile organic compounds in sequence to verify the extraction performance of this porous headspace solid‐phase microextraction probe. It was found that the analysis method combining a headspace solid‐phase microextraction probe and gas chromatography with mass spectrometry yielded determination coefficients of no less than 0.985 and relative standard deviations of 4.3–12.4%. The porous headspace solid‐phase microextraction probe showed no decrease of extraction ability after 200 uses. These results demonstrate that the packed extraction probe with porous structure can be used for headspace solid‐phase microextraction. This novel design may overcome both the stripping and breakage problems of the conventional coating fiber.     

Polyaniline‐coated cigarette filters as a solid‐phase extraction sorbent for the extraction and enrichment of polycyclic aromatic hydrocarbon in water samples

Polyaniline coated cigarette filters were successfully synthesized and used as a solid‐phase extraction sorbent for the extraction and preconcentration of polycyclic aromatic hydrocarbons in water samples. The polyaniline helped to enhance the adsorption ability of polycyclic aromatic hydrocarbons on the sorbent through π–π interactions. The high porosity and large surface area of the cigarette filters helped to reduce backpressure and can be operated with high sample flow rate without loss of extraction efficiency. The developed sorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The parameters that affected the extraction efficiencies, i.e. polymerization time, type of desorption solvent and its volume, sample flow rate, sample volume, sample pH, ionic strength, and organic modifier were investigated. Under the optimal conditions, the method was linear over the range of 0.5–10 μg/L and a detection limit of 0.5 ng/L. This simple, rapid, and cost‐effective method was successfully applied to the preconcentration of polycyclic aromatic hydrocarbons from water samples. The developed method provided a high enrichment factor with good extraction efficiency (85–98%) and a relative standard deviation <10%.     

Polymeric ionic liquid modified stainless steel wire as a novel fiber for solid‐phase microextraction

A polymeric ionic liquid modified stainless steel wire for solid‐phase microextraction was reported. Mercaptopropyl‐functionalized stainless steel wire that was formed by co‐condensation of tetramethoxysilane and 3‐mercaptopropyltrimethoxysilane via a sol‐gel process, which is followed by in situ surface radical chain‐transfer polymerization of 1‐vinyl‐3‐octylimidazolium hexafluorophosphate to result in polymeric ionic liquid modified stainless steel wire. The fiber surface was characterized by field emission scanning electron microscope equipped with energy dispersive X‐ray analysis. Coupled with GC, extraction performance of the fiber was tested with phenols and polycyclic aromatic hydrocarbons as model analytes. Effects of extraction and desorption conditions were investigated systematically in our work. RSDs for single‐fiber repeatability and fiber‐to‐fiber reproducibility were less than 7.34 and 16.82%, respectively. The calibration curves were linear in a wide range for all analytes and the detection limits were in the range of 10–60 ng L^?1. Two real water samples from the Yellow River and local waterworks were applied to test the as‐established solid‐phase microextraction–GC method with the recoveries of samples spiked at 10 μg L^?1 ranged from 83.35 to 119.24%. The fiber not only exhibited excellent extraction efficiency, but also very good rigidity, stability and durability.     

Silicon carbide nanomaterial as a coating for solid‐phase microextraction

Silicon carbide has excellent properties, such as corrosion resistance, high strength, oxidation resistance, high temperature, and so on. Based on these properties, silicon carbide was coated on stainless‐steel wire and used as a solid‐phase microextraction coating, and polycyclic aromatic hydrocarbons were employed as model analytes. Using gas chromatography, some important factors that affect the extraction efficiency were optimized one by one, and an analytical method was established. The analytical method showed wide linear ranges (0.1–30, 0.03–30, and 0.01–30 μg/L) with satisfactory correlation coefficients (0.9922–0.9966) and low detection limits (0.003–0.03 μg/L). To investigate the practical application of the method, rainwater and cigarette ash aqueous solution were collected as real samples for extraction and detection. The results indicate that silicon carbide has excellent application in the field of solid‐phase microextraction.     

Development of a solid‐phase microextraction fiber by the chemical binding of graphene oxide on a silver‐coated stainless‐steel wire with an ionic liquid as the crosslinking agent

Graphene oxide was bonded onto a silver‐coated stainless‐steel wire using an ionic liquid as the crosslinking agent by a layer‐by‐layer strategy. The novel solid‐phase microextraction fiber was characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and Raman microscopy. A multilayer graphene oxide layer was closely coated onto the supporting substrate. The thickness of the coating was about 4 μm. Coupled with gas chromatography, the fiber was evaluated using five polycyclic aromatic hydrocarbons (fluorene, anthracene, fluoranthene, 1,2‐benzophenanthrene, and benzo(a)pyrene) as model analytes in direct‐immersion mode. The main conditions (extraction time, extraction temperature, ionic strength, and desorption time) were optimized by a factor‐by‐factor optimization. The as‐established method exhibited a wide linearity range (0.5–200 μg/L) and low limits of determination (0.05–0.10 μg/L). It was applied to analyze environmental water samples of rain and river water. Three kinds of the model analytes were quantified and the recoveries of samples spiked at 10 μg/L were in the range of 92.3–120 and 93.8–115%, respectively. The obtained results indicated the fiber was efficient for solid‐phase microextraction analysis.     

Optimization of multiwalled carbon nanotubes reinforced hollow‐fiber solid–liquid‐phase microextraction for the determination of polycyclic aromatic hydrocarbons in environmental water samples using experimental design

A novel design of hollow‐fiber liquid‐phase microextraction containing multiwalled carbon nanotubes as a solid sorbent, which is immobilized in the pore and lumen of hollow fiber by the sol–gel technique, was developed for the pre‐concentration and determination of polycyclic aromatic hydrocarbons in environmental water samples. The proposed method utilized both solid‐ and liquid‐phase microextraction media. Parameters that affect the extraction of polycyclic aromatic hydrocarbons were optimized in two successive steps as follows. Firstly, a methodology based on a quarter factorial design was used to choose the significant variables. Then, these significant factors were optimized utilizing central composite design. Under the optimized condition (extraction time = 25 min, amount of multiwalled carbon nanotubes = 78 mg, sample volume = 8 mL, and desorption time = 5 min), the calibration curves showed high linearity (R ² = 0.99) in the range of 0.01–500 ng/mL and the limits of detection were in the range of 0.007–1.47 ng/mL. The obtained extraction recoveries for 10 ng/mL of polycyclic aromatic hydrocarbons standard solution were in the range of 85–92%. Replicating the experiment under these conditions five times gave relative standard deviations lower than 6%. Finally, the method was successfully applied for pre‐concentration and determination of polycyclic aromatic hydrocarbons in environmental water samples.     

An in‐needle solid‐phase microextraction device packed with etched steel wires for polycyclic aromatic hydrocarbons enrichment in water samples

A novel, low‐cost and effective in‐needle solid‐phase microextraction device was developed for the enrichment of trace polycyclic aromatic hydrocarbons in water samples. The in‐needle solid‐phase microextraction device could be easily assembled by inserting hydrofluoric acid‐etched wires, which were used as adsorbent, into a 22‐gauge needle tube within spring supporters. Compared with the commercial solid‐phase microextraction fiber, the developed device has higher efficiency for the extraction of polycyclic aromatic hydrocarbons with four to six rings from water samples using the optimized extraction conditions. With gas chromatography equipped with a flame ionization detector, the limits of detection for the polycyclic aromatic hydrocarbons with four to six rings ranged from 0.0020 to 0.0067 ng/mL. The relative standard deviations for one needle and needle‐to‐needle extractions were in the range of 5.2–9.9% (n = 5) and 3.4–12.3% (n = 5), respectively. The spiked recoveries of the polycyclic aromatic hydrocarbons in tap water samples ranged from 73.2 to 95.4%. This in‐needle solid‐phase microextraction device could be a good field sampler because of the low sample loss over a long storage time.     

Determination of trace hydroxyl polycyclic aromatic hydrocarbons in urine using graphene oxide incorporated monolith solid‐phase extraction coupled with LC‐MS/MS

The biomonitoring of hydroxy polycyclic aromatic hydrocarbons in urine, as a direct way to access multiple exposures to polycyclic aromatic hydrocarbons, has raised great concerns due to their increasing hazardous health effects on humans. Solid‐phase extraction is an effective and useful technique to preconcentrate trace analytes from biological samples. Here, we report a novel solid‐phase extraction method using a graphene oxide incorporated monolithic syringe for the determination of six hydroxy polycyclic aromatic hydrocarbons in urine coupled with liquid chromatography‐tandem mass spectrometry. The effect of graphene oxide amount, washing solvent, eluting solvent, and its volume on the extraction performance were investigated. The fabricated monoliths gave higher adsorption efficiency and capacity than the neat polymer monolith and commercial C₁₈ sorbent. Under the optimum conditions, the developed method provided the detection limits (S/N = 3) of 0.02–0.1 ng/mL and the linear ranges of 0.1–1500 ng/mL for six analytes in urine sample. The recoveries at three spiked levels ranged from 77.5 to 97.1%. Besides, the intra column‐to‐column (n = 3) and inter batch‐to‐batch (n = 3) precisions were ≤ 9.8%. The developed method was successfully applied for the determination of hydroxy polycyclic aromatic hydrocarbons in urine samples of coke oven workers.     

Cadmium sulfide nanoparticles as a novel coating for solid‐phase microextraction

CdS nanoparticles coated on a stainless‐steel wire for solid‐phase microextraction was prepared. Scanning electron microscopy showed that the CdS nanoparticles clustered together to form a porous structure and X‐ray diffraction confirmed that the CdS nanoparticles were the wurtzite phase. Coupled to gas chromatography with flame ionization detection, the extraction abilities of the fiber for polycyclic aromatic hydrocarbons were examined by the headspace method. The parameters of adsorption time, adsorption temperature, salt concentration, desorption time, and desorption temperature were investigated and optimized. For the method, wide linearity and low limits of detection from 5 to 15 ng/L were obtained. The relative standard deviations for single‐fiber repeatability and fiber‐to‐fiber reproducibility were less than 10.2 and 12.6%, respectively. The enrichment factors were from 1155.6 to 3905.4, showing the fiber has good extraction capacity for polycyclic aromatic hydrocarbons. Moreover, the fiber can be used more than 50 times, exhibiting good stability. The established method was also used to analyze the polycyclic aromatic hydrocarbons in two real samples, and the recoveries from 82.7 to 114.2% further proved the reliability of the method.     

Graphene oxide decorated with silver nanoparticles as a coating on a stainless‐steel fiber for solid‐phase microextraction

A novel graphene oxide decorated with silver nanoparticles coating on a stainless‐steel fiber for solid‐phase microextraction was prepared. Scanning electron microscopy and X‐ray photoelectron spectroscopy were used to characterize the coating surface and showed that silver nanoparticles were dispersed on the wrinkled graphene oxide surface. Coupled to gas chromatography with flame ionization detection, the extraction abilities of the fiber for polycyclic aromatic hydrocarbons were examined in the headspace solid‐phase microextraction mode. The extraction parameters including adsorption time, adsorption temperature, salt concentration, desorption time and desorption temperature were investigated. Under the optimized condition, wide linearity with low limits of detection from 2 to 10 ng/L was obtained. The relative standard deviations for single‐fiber repeatability and fiber‐to‐fiber reproducibility were less than 10.6 and 17.5%, respectively. The enrichment factors were from 1712.5 to 4503.7, showing the fiber has good extraction abilities. Moreover, the fiber exhibited a good stability and could be reused for more than 120 times. The established method was also applied for determination of polycyclic aromatic hydrocarbons in two real water samples and the recoveries of analytes ranged from 84.4–116.3% with relative standard deviations less than 16.2%.     

Loading controlled magnetic carbon dots for microwave‐assisted solid‐phase extraction: Preparation,extraction evaluation and applications in environmental aqueous samples

An adsorbent of carbon dot@poly(glycidyl methacrylate)@Fe₃O₄ nanoparticles has been developed for the microwave‐assisted magnetic solid‐phase extraction of polycyclic aromatic hydrocarbons in environmental aqueous samples prior to high‐performance liquid chromatography with UV/visible spectroscopy detection. Poly(glycidyl methacrylate) was synthesized by atom transfer radical polymerization. The chain length and amount of carbon dots attached on them can be easily controlled through changing polymerization conditions, which contributes to tunable extraction performance. The successful fabrication of the nano‐adsorbent was confirmed by transmission electronic microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and vibrating sample magnetometry. The extraction performance of the adsorbent was evaluated by using polycyclic aromatic hydrocarbons as model analytes. The key factors influencing the extraction, such as microwave power, adsorption time, desorption time and desorption solvents were investigated in detail. Under the optimal conditions, the microwave‐assisted method afforded magnetic solid‐phase extraction with short extraction time, wide dynamic linear range (0.02–200 μg/L), good linearity (R² ≥ 98.57%) and low detection limits (20–90 ng/L) for model analytes. The adsorbent was successfully applied for analyzing polycyclic aromatic hydrocarbons in environmental aqueous samples and the recoveries were in the range of 86.0–124.2%. Thus, the proposed method is a promising candidate for fast and reliable preconcentration of trace polycyclic aromatic hydrocarbons in real water samples.     

Palladium‐coated stainless‐steel wire as a solid‐phase microextraction fiber

A novel palladium solid‐phase microextraction coating was fabricated on a stainless‐steel wire by a simple in situ oxidation–reduction process. The palladium coating exhibited a rough microscaled surface and its thickness was about 2 μm. Preparation conditions (reaction time and concentration of palladium chloride and hydrochloric acid) were optimized in detail to achieve sufficient extraction efficiency. Extraction properties of the fiber were investigated by direct immersion solid‐phase microextraction of several polycyclic aromatic hydrocarbons and phthalate esters in aqueous samples. The extracted analytes were transferred into a gas chromatography system by thermal desorption. The effect of extraction and desorption conditions on extraction efficiency were investigated. Under the optimum conditions, good linearity was obtained and correlation coefficients between 0.9908 and 0.9990 were obtained. Limits of detection were 0.05–0.10 μg/L for polycyclic aromatic hydrocarbons and 0.3 μg/L for phthalate esters. Their recoveries for real aqueous samples were in the range from 97.1 to 121% and from 89.1 to 108%, respectively. The intra‐ and interday tests were also investigated with three different addition levels, and satisfactory results were also obtained.     

Inorganic–organic hybrid coating material for the online in‐tube solid‐phase microextraction of monohydroxy polycyclic aromatic hydrocarbons in urine

An inorganic–organic hybrid nanocomposite (zinc oxide/polypyrrole) that represents a novel kind of coating for in‐tube solid‐phase microextraction is reported. The composite coating was prepared by a facile electrochemical polymerization strategy on the inner surface of a stainless‐steel tube. Based on the coated tube, a novel online in‐tube solid‐phase microextraction with liquid chromatography and mass spectrometry method was developed and applied for the extraction of three monohydroxy polycyclic aromatic hydrocarbons in human urine. The coating displayed good extraction ability toward monohydroxy polycyclic aromatic hydrocarbons. In addition, long lifespan, excellent stability, and good compression resistance were also obtained for the coating. The experimental conditions affecting the extraction were optimized systematically. Under the optimal conditions, the limits of detection and quantification were in the range of 0.039–0.050 and 0.130–0.167 ng/mL, respectively. Good linearity (0.2–100 ng/mL) was obtained with correlation coefficients larger than 0.9967. The repeatability, expressed as relative standard deviation, ranged between 2.5% and 9.4%. The method offered the advantage of process simplicity, rapidity, automation, and sensitivity in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities of Hubei province. An acceptable recovery of monohydroxy polycyclic aromatic hydrocarbons (64–122%) represented the additional attractive features of the method in real urine analysis.     

Solid‐phase microextraction with a graphene‐composite‐coated fiber coupled with GC for the determination of some halogenated aromatic hydrocarbons in water samples

In this work, a graphene composite was coated onto etched stainless‐steel wire through a sol–gel technique and it was used as a solid‐phase microextraction (SPME) fiber. The prepared fiber was characterized by SEM, which revealed that the fiber had a highly porous structure. The application of the fiber was evaluated through the headspace SPME of five halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, 1,3‐dichlorobenzene, 1,2‐dichlorobenzene, and 1,2,4‐trichlorobenzene) in water samples followed by GC with flame ionization detection. The main factors influencing the extraction efficiency, including headspace volume, extraction time, extraction temperature, stirring rate, ionic strength of sample solution, and desorption conditions, were studied and optimized. Under the optimum conditions, the linearity of the method ranged from 2.5 to 800.0 μg/L for 1,2,4‐trichlorobenzene and from 2.5 to 500.0 μg/L for chlorobenzene, bromobenzene, 1,3‐dichlorobenzene, and 1,2‐dichlorobenzene, with the correlation coefficients (r) ranging from 0.9962 to 0.9980, respectively. The LODs (S/N = 3) of the method for the analytes were in the range between 0.5 and 1.0 μg/L. The recoveries of the method for the analytes obtained for the spiked water samples at 50.0 and 250.0 μg/L were from 76.0 to 104.0%.