Determination of phthalate esters from environmental water samples by micro‐solid‐phase extraction using TiO2 nanotube arrays before high‐performance liquid chromatography

We describe a highly sensitive micro‐solid‐phase extraction method for the pre‐concentration of six phthalate esters utilizing a TiO₂ nanotube array coupled to high‐performance liquid chromatography with a variable‐wavelength ultraviolet visible detector. The selected phthalate esters included dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, bis(2‐ethylhexyl)phthalate and dioctyl phthalate. The factors that would affect the enrichment, such as desorption solvent, sample pH, salting‐out effect, extraction time and desorption time, were optimized. Under the optimum conditions, the linear range of the proposed method was 0.3–200 μg/L. The limits of detection were 0.04–0.2 μg/L (S/N = 3). The proposed method was successfully applied to the determination of six phthalate esters in water samples and satisfied spiked recoveries were achieved. These results indicated that the proposed method was appropriate for the determination of trace phthalate esters in environmental water samples.     

Nanostructured copper‐coated solid‐phase microextraction fiber for gas chromatographic analysis of dibutyl phthalate and diethylhexyl phthalate environmental estrogens

A novel nanostructured copper‐based solid‐phase microextraction fiber was developed and applied for determining the two most common types of phthalate environmental estrogens (dibutyl phthalate and diethylhexyl phthalate) in aqueous samples, coupled to gas chromatography with flame ionization detection. The copper film was coated onto a stainless‐steel wire via an electroless plating process, which involved a surface activation process to improve the surface properties of the fiber. Several parameters affecting extraction efficiency such as extraction time, extraction temperature, ionic strength, desorption temperature, and desorption time were optimized by a factor‐by‐factor procedure to obtain the highest extraction efficiency. The as‐established method showed wide linear ranges (0.05–250 μg/L). Precision of single fiber repeatability was <7.0%, and fiber‐to‐fiber repeatability was <10%. Limits of detection were 0.01 μg/L. The proposed method exhibited better or comparable extraction performance compared with commercial and other lab‐made fibers, and excellent thermal stability and durability. The proposed method was applied successfully for the determination of model analytes in plastic soaking water.     

Solid‐phase extraction based on chloromethylated polystyrene magnetic nanospheres followed by gas chromatography with mass spectrometry to determine phthalate esters in beverages

An ultrasound‐assisted magnetic solid‐phase extraction procedure with chloromethylated polystyrene‐coated Fe₃O₄ nanospheres as magnetic adsorbents has been developed to determine eight phthalate esters (bis(4‐methyl‐2‐pentyl) phthalate, dipentyl phthalate, dihexyl phthalate, benzyl butyl phthalate, bis(2‐butoxyethyl) phthalate, dicyclohexyl phthalate, di‐n‐octyl phthalate, and dinonyl phthalate) simultaneously in beverage samples, in combination with gas chromatography coupled to tandem mass spectrometry for the first time. Several factors related to magnetic solid‐phase extraction efficiencies, such as amount of adsorbent, extracting time, ionic strength, and desorption conditions were investigated. The enrichment factors of the method for the eight analytes were over 2482. A good linearity was observed in the range of 10–500 ng/L for bis(2‐butoxyethyl) phthalate and 2–500 ng/L for the other phthalate esters with correlation coefficients ranging from 0.9980 to 0.9998. The limits of detection and quantification for the eight phthalate esters were in the range of 0.20–2.90 and 0.67–9.67 ng/L, respectively. The mean recoveries at three spiked levels were 75.8–117.7%, the coefficients of variations were <11.6%. The proposed method was demonstrated to be a simple and efficient technique for the trace analysis of the phthalate esters in beverage samples.     

Simultaneous determination of phthalates and adipates in human serum using gas chromatography–mass spectrometry with solid‐phase extraction

A gas chromatography–mass spectrometry assay was developed and validated for the simultaneous determination of phthalates and adipates in human serum. The phthalates and adipates studied were dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzylbutyl phthalate, di‐2‐ethylhexyl phthalate, di‐n‐octyl phthalate, diethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2‐butoxyethyl) adipate and di‐2‐ethylhexyl adipate, with diisooctyl phthalate as internal standard. The extraction and cleaning up procedure was carried out with solid‐phase extraction cartridges containing dimethyl butylamine groups, which showed extraction efficiencies over 88% for each analyte and the internal standard. The calibration curves obtained were linear with correlation coefficients greater than 0.98. For all analytes, the assay gave CV% values for intra‐day precision from 4.9 to 13.3% and mean accuracy values from 91.4 to 108.4%, while inter‐day precision was 5.2–13.4% and mean accuracy 91.0–110.2%. The limits of detection for the assay of phthalates and adipates were in the range 0.7–4.5 ng/mL. The method is simple, sensitive and accurate, and allows for simultaneous determination of nanogram levels of phthalates and adipates in human serum. It was successfully applied to an investigation on the level of phthalates and adipates in a non‐occupationally exposed population.     

A porous carbon derived from amino‐functionalized material of Institut Lavoisier as a solid‐phase microextraction fiber coating for the extraction of phthalate esters from tea

In this work, a porous carbon derived from amino‐functionalized material of Institut Lavoisier (C‐NH₂‐MIL‐125) was prepared and coated onto a stainless‐steel wire through sol–gel technique. The coated fiber was used for the solid‐phase microextraction of trace levels of phthalate esters (diallyl phthalate, di‐iso‐butyl ortho‐phthalate, di‐n‐butyl ortho‐phthalate, benzyl‐n‐butyl ortho‐phthalate, and bis(2‐ethylhexy) ortho‐phthalate) from tea beverage samples before gas chromatography with mass spectrometric analysis. Several experimental parameters that could influence the extraction efficiency such as extraction time, extraction temperature, sample pH, sample salinity, stirring rate, desorption temperature and desorption time, were investigated. Under the optimal conditions, the linearity existed in the range of 0.05–30.00 μg/L for green jasmine tea beverage samples, and 0.10–30.00 μg/L for honey jasmine tea beverage samples, with the correlation coefficients (r) ranging from 0.9939 to 0.9981. The limits of detection of the analytes for the method were 2.0–3.0 ng/L for green jasmine tea beverage sample, and 4.0–5.0 ng/L for honey jasmine tea beverage sample, depending on the compounds. The recoveries of the analytes for the spiked samples were in the range of 82.0–106.0%, and the precision, expressed as the relative standard deviations, was less than 11.1%.     

Application of magnetized MOF‐74 to phthalate esters extraction from Chinese liquor

In this study, magnetized MOF‐74 (Ni) was prepared using an ultrasound‐assisted synthesis method. This novel functional magnetic adsorbent was characterized using various techniques. Using the prepared material as adsorbents, a magnetic solid‐phase extraction method coupled with high‐performance liquid chromatography was proposed for determining four phthalate esters in Chinese liquor samples. The extraction parameters, including solution pH, adsorbent amount, extraction time, and eluent type and volume, were optimized. Under the optimized conditions, proposed method showed good linearity within the range of 1.53–200 μg/L for diphenyl phthalate, 2.03–200 μg/L for butyl benzyl phthalate, 7.02–200 μg/L for diamyl phthalate, and 6.03–200 μg/L for dicyclohexyl phthalate, with correlation coefficients > 0.9944, low limits of detection (0.46–2.10 μg/L, S/N = 3), and good extraction repeatability (relative standard deviations of 3.7%, n = 6). This method was successfully used to analyze phthalate esters in Chinese liquor samples with recoveries of 74.4–104.8%. Two phthalate esters were detected in two samples, both at concentrations that satisfied the Chinese national standard, indicating this method has practical application prospects. The extraction efficiency of this method was also compared with conventional solid‐phase extraction using commercial C₁₈ cartridges. The results demonstrated that the proposed magnetic solid‐phase extraction is a simple, time‐saving, efficient, and low‐cost method.     

Analysis of 16 phthalic acid esters in food simulants from plastic food contact materials by LC‐ESI‐MS/MS

An RP LC‐ESI‐MS/MS method for the determination of the migration of 16 primary phthalic acid esters from plastic samples has been developed using distilled water, 3% acetic acid, 10% alcohol, and olive oil as food simulants. Detection limits were 1.6–18.5 μg/kg in distilled water, 1.4–17.3 μg/kg in 3% acetic acid, 1.4–19.2 μg/kg in 10% alcohol, and 31.9–390.8 μg/kg in olive oil. The RSDs were in the range of 0.07–11.28%. The real plastic products inspection showed that only few analyzed samples were phthalates contaminated. Bis‐2‐ethylhexyl ester and dibutyl phthalate were the common items migrated from the plastic products into food and feeds, but the migration concentrations were far below the limits set by European Union (1.5 mg/kg for bis‐2‐ethylhexyl ester and 0.3 mg/kg for dibutyl phthalate).     

Determination of phthalate esters in bottled water using dispersive liquid–liquid microextraction coupled with GC–MS

Dispersive liquid–liquid microextraction method was developed for the determination of the amount of phthalate esters in bottled drinking water samples and dispersive liquid–liquid microextraction samples were analyzed by GC–MS. Various experimental conditions influencing the extraction were optimized. Under the optimized conditions, very good linearity was observed for all analytes in a range between 0.05 and 150 μg/L with coefficient of determination (R²) between 0.995 and 0.999. The LODs based on S/N = 3 were 0.005–0.22 μg/L. The reproducibility of dispersive liquid–liquid microextraction was evaluated. The RSDs were 1.3–5.2% (n = 3). The concentrations of phthalates were determined in bottled samples available in half shell. To understand the leaching profile of these phthalates from bottled water, bottles were exposed to direct sunlight during summer (temperature from 34–57°C) and sampled at different intervals. Result showed that the proposed dispersive liquid–liquid microextraction is suitable for rapid determination of phthalates in bottled water and di‐n‐butyl, butyl benzyl, and bis‐2‐ethylhexyl phthalate compounds leaching from bottles up to 36 h. Thereafter, degradation of phthalates was observed.     

Application of magnetic graphitic carbon nitride nanocomposites for the solid‐phase extraction of phthalate esters in water samples

Magnetic graphitic carbon nitride nanocomposites were successfully prepared in situ and used to develop a highly sensitive magnetic solid‐phase extraction method for the preconcentration of phthalate esters such as di‐n‐butyl phthalate, butyl phthalate, dihexyl phthalate, and di‐(2‐ethyl hexyl) phthalate from water. The adsorption and desorption of the phthalate esters on magnetic graphitic carbon nitride nanocomposites were investigated and the parameters affecting the partition of the phthalate esters, such as adsorption, desorption, recovery, were assessed. Under the optimized conditions, the proposed method showed excellent sensitivity with limits of detection (S/N = 3) in the range of 0.05–0.1 μg/L and precision in the range of 1.1–2.6% (n = 5). This method was successfully applied to the analysis of real water samples, and good spiked recoveries over the range of 79.4–99.4% were obtained. This research provides a possibility to apply this nanocomposite for adsorption, preconcentration, or even removal of various carbon‐based ring or hydrophobic pollutants.     

Solid‐based disperser liquid–liquid microextraction for the preconcentration of phthalate esters and di‐(2‐ethylhexyl) adipate followed by gas chromatography with flame ionization detection or mass spectrometry

A new approach for the development of a dispersive liquid–liquid microextraction followed by GC with flame ionization detection was proposed for the determination of phthalate esters and di‐(2‐ethylhexyl) adipate in aqueous samples. In the proposed method, solid and liquid phases were used as the disperser and extractant, respectively, providing a simple and fast mode for the extraction of the analytes into a small volume of an organic solvent. In this method, microliter levels of an extraction solvent was added onto a sugar cube and it was transferred into the aqueous phase containing the analytes. By manual shaking, the sugar was dissolved and the extractant was released into the aqueous phase as very tiny droplets to provide a cloudy solution. Under optimized conditions, the proposed method showed good precision (RSD less than 5.2%), high enrichment factors (266–556), and low LODs (0.09–0.25 μg/L). The method was successfully applied for the determination of the target analytes in different samples, and good recoveries (71–103%) were achieved for the spiked samples. No need for a disperser solvent and higher enrichment factors compared with conventional dispersive liquid–liquid microextraction and low cost and short sample preparation time are other advantages of the method.     

Preparation of magnetic molecularly imprinted polymer nanoparticles by surface imprinting by a sol–gel process for the selective and rapid removal of di‐(2‐ethylhexyl) phthalate from aqueous solution

Magnetic molecularly imprinted polymer nanoparticles for di‐(2‐ethylhexyl) phthalate were synthesized by surface imprinting technology with a sol–gel process and used for the selective and rapid adsorption and removal of di‐(2‐ethylhexyl) phthalate from aqueous solution. The prepared magnetic molecularly imprinted polymer nanoparticles were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and vibrating sample magnetometry. The adsorption of di‐(2‐ethylhexyl) phthalate onto the magnetic molecularly imprinted polymer was spontaneous and endothermic. The adsorption equilibrium was achieved within 1 h, the maximum adsorption capacity was 30.7 mg/g, and the adsorption process could be well described by Langmuir isotherm model and pseudo‐second‐order kinetic model. The magnetic molecularly imprinted polymer displayed a good adsorption selectivity for di‐(2‐ethylhexyl) phthalate with respect to dibutyl phthalate and di‐n‐octyl phthalate. The reusability of magnetic molecularly imprinted polymer was demonstrated for at least eight repeated cycles without significant loss in adsorption capacity. The adsorption efficiencies of the magnetic molecularly imprinted polymer toward di‐(2‐ethylhexyl) phthalate in real water samples were in the range of 98–100%. These results indicated that the prepared adsorbent could be used as an efficient and cost‐effective material for the removal of di‐(2‐ethylhexyl) phthalate from environmental water samples.     

Simultaneous determination of five phthalate esters and bisphenol A in milk by packed‐nanofiber solid‐phase extraction coupled with gas chromatography and mass spectrometry

A novel polystyrene/pyridine composite nanofiber was synthesized and utilized as the sorbent material for the solid‐phase extraction of bisphenol A and five common phthalate esters in milk. The method of extraction integrated extraction and preconcentration of target analytes into a single step. Bisphenol A and five common phthalate esters were selected as target compounds for the development and evaluation of the method. The effects of operating parameters for nanofiber‐based solid‐phase extraction, such as selection and amount of sorbent, the volume fraction of perchlorate (precipitate protein), desorption solvent, volume of desorption solvent, and effect of salt addition were optimized. Under optimal conditions, higher extraction recoveries (89.6–118.0%) of the six compounds in milk spiked at three levels were obtained, and the satisfied relative standard deviation were ranged from 0.6 to 10.9%. The detection limits and quantification limits of the method ranged from 0.01 to 0.06 μg/L and 0.05 to 0.53 μg/L, respectively. Matrix effects were also verified and well controlled in the range of 91.3–109.3%. The new method gave better performance metrics than Chinese standard method and other published methods. Thus, the proposed method may be applied to the analysis of the phthalate esters and bisphenol A in complex matrixes.     

Solvent‐vapor‐assisted liquid–liquid microextraction: A novel method for the determination of phthalate esters in aqueous samples using GC–MS

A novel liquid–liquid microextraction method, namely, solvent‐vapor‐assisted liquid–liquid microextraction for the determination of dimethyl phthalate, diethyl phthalate, dibutyl phthalate and bis(2‐ethylhexyl) phthalate in the aqueous samples using gas chromatography with mass spectrometry was developed. In the proposed method, extracting solvent was heated, and solvent vapor as the extracting phase was injected into the sample solution. As a result of the low temperature of the sample solution and higher density of the extracting phase than the aqueous medium, solvent vapor was condensed and an organic‐phase drop formed in the bottom of sample tube. Because of the gas status of the extracting solvent, the surface area between the extracting solvent and the aqueous sample was remarkably high. Under the optimized conditions, tetrachloride carbon was used as an extracting solvent. The method shows high coefficient of determination (R ²) values in the range of 0.5–200 and 1.0–200 ng/mL for the target analytes. Enrichment factors and limits of detection for the studied phthalates are obtained in the ranges of 2800–3000 and 0.15–0.3 ng/mL, respectively. Recoveries and relative standard deviations were in the range of 80.0–100.0 and 2.2–7.8%, respectively. The proposed method successfully used for analysis of several aqueous samples.     

Dicationic polymeric ionic‐liquid‐based magnetic material as an adsorbent for the magnetic solid‐phase extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons

Magnetic particles modified with a dicationic polymeric ionic liquid are described as a new adsorbent in magnetic solid‐phase extraction. They were obtained through the copolymerization of a 1,8‐di(3‐vinylimidazolium)octane‐based ionic liquid with vinyl‐modified SiO₂@Fe₃O₄, and were characterized by FTIR spectroscopy, X‐ray diffraction, and vibrating sample magnetometry. The modified magnetic particles are effective in the extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons. Also, they can provide different extraction performance for the selected analytes including fenitrothion, parathion, fenthion, phoxim, phenanthrene, and fluoranthene, where the extraction efficiency is found to be in agreement with the hydrophobicity of analytes. Various factors influencing the extraction efficiency, such as, the amount of adsorbent, extraction, and desorption time, and type and volume of the desorption solvent, were optimized. Under the optimized conditions, a good linearity ranging from 1–100 μg/L is obtained for all analytes, except for parathion (2–200 μg/L), where the correlation coefficients varied from 0.9960 to 0.9998. The limits of detection are 0.2–0.8 μg/L, and intraday and interday relative standard deviations are 1.7–7.4% (n = 5) and 3.8–8.0% (n = 3), respectively. The magnetic solid‐phase extraction combined with high‐performance liquid chromatography can be applied for the detection of trace targets in real water samples with satisfactory relative recoveries and relative standard deviations.     

Determination of Phthalates in Milk by Ultrasound-Assisted Dispersive Liquid–Liquid Microextraction and Gas Chromatography–Mass Spectrometry

Ultrasound-assisted dispersive liquid–liquid microextraction was coupled with gas chromatography—mass spectrometry for the determination of phthalate esters in milk. Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate, and dioctyl phthalate were analyzed in five brands of pasteurized Turkish milk. The efficiencies of the extraction procedure for the analytes were between 66 and 100%. The linear dynamic ranges of the calibration curves were from 0.025 to 1.000 µg/mL with correlation coefficients exceeding 0.99. The precision of the method is acceptable with relative standard deviation values below 5%. Dibutyl phthalate and bis(2-ethylhexyl) phthalate were commonly observed in milk.     

pH‐assisted homogeneous liquid–liquid microextraction using dialkylphosphoric acid as an extraction solvent for the determination of chlorophenols in water samples

In this study, a new pH‐assisted homogeneous liquid–liquid microextraction combined with HPLC with UV detection was developed for the determination of chlorophenols in water samples. In this approach, bis(2‐ethylhexyl) phosphate was used for the first time as the low‐density extraction solvent. In particular, 60 μL of bis(2‐ethylhexyl) phosphate was injected into the sample solution (5 mL) and dissolved completely in the sample solution while the pH was increased to 9. Afterwards, the pH of the sample solution was lowered to 1, and a cloudy solution was formed. At this stage, hydrophobic interactions between the analytes and the long double hydrocarbon chains of extraction solvent were expected to be the main forces driving extraction. A series of parameters that influence extraction were investigated systematically. Under the optimized conditions, the LODs and LOQs for the chlorophenols were 1.4–2.7 and 4.7–9.1 ng/mL, respectively. RSDs based on five replicate extraction of 100 ng/mL of each chlorophenols were <4.7% for intraday and 7.4% for interday precision. This method has been also successfully applied to analyze real water samples at two different spiked concentrations, and satisfactory recoveries were achieved.     

Mesoporous Silica‐coated Magnetic Nanoparticles for Mixed Hemimicelles Solid‐phase Extraction of Phthalate Esters in Environmental Water Samples with Liquid Chromatographic Analysis

To extract, preconcentrate and determine the trace level of environmental contaminants, a novel mixed hemimicelles solid‐phase extraction (MHSPE) method based on mesoporous silica‐coated magnetic nanoparticles (Fe₃O₄/meso‐SiO₂ NPs) as adsorbent was developed for extraction of phthalate esters from water samples. The Fe₃O₄/meso‐SiO₂ NPs were synthesized by using a combination of hydrothermal method and sol‐gel method. The obtained Fe₃O₄/meso‐SiO₂ NPs possessed a large surface area (570 m²/g), superparamagnetism, and uniform mesopores (2.8 nm). MHSPE parameters, such as the amount of surfactant, pH of sample, shaking and separation time, eluent and breakthrough volume that may influence the extraction of analytes greatly, were further investigated. Under the optimized conditions, the extraction was completed in 20 min and a concentration factor of 500 was achieved by extracting 250 mL water sample. Detection limits obtained of butyl‐benzyl phthalate (BBP), di‐n‐butyl phthalate (DnBP), di‐(2‐ethylhexyl) phthalate (DEHP) and di‐n‐cotyl phthalate (DnOP) were 12, 21, 12, and 32 ng/L, respectively. The proposed method exhibited high extraction efficiency and relatively short time for extracting the target compounds.     

Nanostructured gemini‐based supramolecular solvent coupled with ultrasound‐assisted back extraction as a preconcentration step before GC–MS

Liquid‐phase microextraction based on gemini‐based supramolecular solvent was successfully applied as a preconcentration step before gas chromatography with mass spectrometry. To eliminate the interferences of gemini surfactant, the analytes were back‐extracted into an immiscible organic solvent in the presence of ultrasonic sound waves. Three phthalate esters (di‐n‐butyl‐, butylbenzyl‐, bis(2‐ethylhexyl)‐, and di‐n‐octyl phthalatic esters) were used as target analytes. The effective parameters on extraction efficiency of the target analytes (i.e., the amount of surfactant and volume of propanol as major components making up the supramolecular solvent, ionic strength, hexane volume, and ultrasound time) were investigated and optimized by a one‐variable‐at‐a‐time method. Under the optimum conditions, the preconcentration factors of the analytes were in the range of 95–182. The linear dynamic range of 0.05–200.00 μg/L with a correlation of determination of (R ²) ≥ 0.9935 was obtained. The proposed method had an excellent limit of detection (S/N = 3) of 0.01 for di‐n‐octyl and 0.02 μg/L for butylbenzyl‐ and di‐n‐butyl‐phthalatic ester. Good relative recoveries in the range of 85.7–105.2% guaranteed the accuracy of the amount of phthalates distinguished in the nonspiked samples.     

Graphene oxide reinforced polymeric ionic liquid monolith solid‐phase microextraction sorbent for high‐performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples

A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1‐(3‐aminopropyl)‐3‐(4‐vinylbenzyl)imidazolium 4‐styrenesulfonate monomer and 1,6‐di‐(3‐vinylimidazolium) hexane bihexafluorophosphate cross‐linking agent. Coupled to high‐performance liquid chromatography, the monolith was used as a solid‐phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5–400 μg/L for 3‐nitrophenol, 2‐nitrophenol, and 2,5‐dichlorophenol and 2–400 μg/L for 4‐chlorophenol, 2‐methylphenol, and 2,4,6‐trichlorophenol (R² = 0.9973–0.9988). The limits of detection were 0.5 μg/L for 3‐nitrophenol and 2‐nitrophenol and 0.2 μg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5–113%.     

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.