Fabrication of boronate‐decorated polyhedral oligomeric silsesquioxanes grafted cotton fiber for the selective enrichment of nucleosides in urine

Various cotton fiber based boronate‐affinity adsorbents are recently developed for the sample pretreatment of cis‐diol‐containing biomolecules, but most do not have efficient capacity due to limited binding sites on the surface of cotton fibers. To increase the density of boronate groups on the surface of cotton fiber, polyhedral oligomeric silsesquioxanes were used to modify cotton fiber to provide plentiful reactive sites for subsequent functionalization with 4‐formylphenylboronic acid. The new adsorbent showed special recognition ability towards cis‐diols and high adsorption capacity (175 μg/g for catechol, 250 μg/g for dopamine, 400 μg/g for adenosine). The in‐pipette‐tip solid‐phase extraction was investigated under different conditions, including pH and ionic strength of solution, adsorbent amount, pipette times, washing solvent, and elution solvent. The in‐pipette‐tip solid‐phase extraction coupled with high‐performance liquid chromatography was used to analyze four nucleosides in urine samples. Under the optimal extraction conditions, the detection limits were determined to be between 5.1 and 6.1 ng/mL (S/N  =  3), and the linearity ranged from 20 to 500 ng/mL for these analytes. The accuracy of the analytical method was examined by studying the relative recoveries of analytes in real urine samples with recoveries varying from 83 to 104% (RSD = 3.9–10.2%, n = 3).     

Determination of organophosphate flame retardants and plasticizers in lipid-rich matrices using dispersive solid-phase extraction as a sample cleanup step and ultra-high performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A fast, robust and highly sensitive analysis method for determination of trace levels of organophosphate ester (OPE) flame retardants and plasticizers in lipid-rich samples was presently developed, and based on ultra-high performance liquid chromatography-tandem mass spectrometry coupled to a positive atmospheric pressure chemical ionization source (UHPLC-MS/MS-APCI(+)). The target OPEs in the sample were extracted from the biota samples, such as egg and liver, by ultrasonic extraction, and cleaned up further by dispersive solid phase extraction (d-ESP). As a result, background contamination was largely reduced. Different dispersive ESP sorbents were tested and primary secondary amine (PSA) bonded silica sorbents showed the best recoveries for these target OPEs. The recoveries obtained were in the range 54–113% (RSD < 17%), with method limits of quantification (MLOQs) ranging between 0.06 and 0.29 ng/g in egg, and 0.05 and 0.50 ng/g w.w. in liver sample. The matrix effects (MEs) associated with using APCI(+) and ESI(+) sources were investigated. APCI(+) showed much less ion suppression than ESI(+) for the determination of these OPEs. For egg and liver samples, the APCI(+) ME values ranged from 40% to 94%, while ESI(+) ME values ranged from 0% to 36%. Although APCI(+) was used for the determination of OPEs, the ionization mechanism might mainly be a thermospray ionization process. This UHPLC-MS/MS-APCI(+) method showed good response linearity for calibration (R2 > 0.99). The proposed method was applied to real environmental bird egg and fish samples, where several OPE were quantifiable and different OPE patterns was observed between samples.     

Miniaturized matrix solid‐phase dispersion coupled with supramolecular solvent‐based microextraction for the determination of paraben preservatives in cream samples

An analytical method is presented for the determination of paraben preservatives in semisolid cream samples by matrix solid‐phase dispersion combined with supramolecular solvent‐based microextraction. Due to the oily and sticky nature of the sample matrix, parabens were first extracted from the samples by matrix solid‐phase dispersion using silica as sorbent material with a clean‐up performed with tetrahydrofuran in the elution step. The eluate (500 μL), 1‐decanol (120 μL), and water (4.4 mL) were then mixed in a polyethylene pipette to form supramolecular solvent. Finally, the analytes in the supramolecular solvent were separated and determined by liquid chromatography with ultraviolet detection. Under optimal extraction conditions, the extraction recoveries of the studied compounds were obtained in the range of 63–83%. The limits of detection for the analytes were between 0.03 and 0.04 μg/g. The precision of the method varied between 4.0–6.7 (intraday) and 6.2–7.9% (interday). Finally, the optimized procedure was applied to the determination of the target preservatives in a variety of cream samples (diaper rash, skin allergy, face and hand moisturizing) with satisfactory recoveries (86–102%).     

Determination of organophosphate flame retardants in soil and fish using ultrasound‐assisted extraction,solid‐phase clean‐up,and liquid chromatography with tandem mass spectrometry

A solid–liquid extraction method in combination with high‐performance liquid chromatography and tandem mass spectrometry was developed and optimized for extraction and analysis of organophosphorus flame retardants in soil and fish. Methanol was chosen as the optimum extraction solvent, not only in terms of extraction efficiency, but also for its broader analyte coverage. The subsequent clean‐up by solid‐phase extraction is required to eliminate matrix coextractives and reduce matrix effects. Recoveries of the optimized method were 50–121% for soil and 47–123% for biota, both with high precision (RSDs <12% in soil and <23% in biota). The method limits of detection ranged from 0.06 to 0.20 ng/g dry weight and between 0.02 and 0.30 ng/g wet weight for soil and biota samples, respectively. However, samples with a high lipid content produce several problems as solid‐phase extraction cartridge clogging that increase variability and analysis time. The method was successfully applied for the determination of organophosphorus flame retardants in soil and fish from L'Albufera Natural Park (Valencia, Spain). Target compounds were detected in all soil and fish samples with values varying from 13.8 to 89.7 ng/g dry weight and from 3.3 to 53.0 ng/g wet weight, respectively.     

A Rapid Method for the Determination of Organochlorine, Pyrethroid Pesticides and Polychlorobiphenyls in Fatty Foods Using GC with Electron Capture Detection

A new, single-step extraction and purification method was developed for the separation of 26 organochlorine pesticides (OCPs), three pyrethroid pesticides (PPs) and six polychlorinated biphenyls (PCBs) from fatty foods of either animal or vegetable origin. The method includes homogenisation of extracted fat and diatomaceous earth. Separation was achieved using a mini Pasteur pipette where a matrix solid-phase dispersion extraction was carried out with only 5 mL of dimethyl sulphoxide as an eluting solvent. A Pasteur pipette was joined to a prepacked slurry filled Florisil column, water deactivated to 15% where a liquid–liquid extraction and adsorption chromatography successively took place. The elution of OCPs, PPs and PCBs was performed with n-hexane/diethyl ether. Recoveries for PCBs were from 81 to 86% and for OCPs 68 to 94%, except for β-HCH, which gave lower, more variable recoveries. Excellent recoveries were obtained for pyrethroid pesticides, mostly more than 80%. The method was applied to 509 fatty samples for monitoring of these compounds. GC, with two columns connected to two electron capture detectors (ECD), was used.     

Simultaneous determination of seven compounds in Chinese patent medicines Chenxiangqu by matrix solid‐phase dispersion coupled with ultra high performance liquid chromatography and quadrupole time‐of‐flight mass spectrometry

A simple, efficient, and sensitive strategy by coupling matrix solid‐phase dispersion with ultra high performance liquid chromatography quadrupole time‐of‐flight mass spectrometry was proposed to extract and determine three types of components (including seven analytes) in Chinese patent medicines Chenxiangqu. The highly ordered mesoporous material Fe‐SBA‐15 synthesized under weakly acidic conditions was selected as a dispersant in matrix solid phase dispersion extraction for the first time. Several parameters including the mass ratio of sample to dispersant, the type of dispersant, the grinding time, and the elution condition were investigated in this work. Under the optimized conditions, 20 compounds were identified by quadrupole time‐of‐flight mass spectrometry and seven analytes were quantified. The results demonstrated that the developed method has good linearity (r > 0.9995), and the limits of detection of the analytes were as low as 0.55 ng/mL. The recoveries of all seven analytes ranged from 97.6 to 104.6% (relative standard deviation < 3.4%). Finally, the improved method was successfully applied to determination of five batches of Chenxiangqu samples, which provided a robust method in quality control of Chinese patent medicines Chenxiangqu. The developed strategy also shows its great potential in analysis of complex matrix samples.     

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.     

MSPD procedure for determining buprofezin,tetradifon, vinclozolin,and bifenthrin residues in propolis by gas chromatography–mass spectrometry

A simple and effective extraction method based on matrix solid-phase dispersion (MSPD) was developed to determine bifenthrin, buprofezin, tetradifon, and vinclozolin in propolis using gas chromatography–mass spectrometry in selected ion monitoring mode (GC–MS, SIM). Different method conditions were evaluated, for example type of solid phase (C₁₈, alumina, silica, and Florisil), the amount of solid phase and eluent (n-hexane, dichloromethane, dichloromethane–n-hexane (8:2 and 1:1, v/v) and dichloromethane–ethyl acetate (9:1, 8:2 and 7:3, v/v)). The best results were obtained using 0.5 g propolis, 1.0 g silica as dispersant sorbent, 1.0 g Florisil as clean-up sorbent, and dichloromethane–ethyl acetate (9:1, v/v) as eluting solvent. The method was validated by analysis of propolis samples fortified at different concentration levels (0.25 to 1.0 mg kg⁻¹). Average recoveries (four replicates) ranged from 67% to 175% with relative standard deviation between 5.6% and 12.1%. Detection and quantification limits ranged from 0.05 to 0.10 mg kg⁻¹ and 0.15 to 0.25 mg kg⁻¹ propolis, respectively.     

Application of a novel nylon needle filter-based solid-phase extraction device to determination of 1-hydroxypyrene in urine

In this work, a simple and miniaturized solid-phase extraction device was constructed by connecting a commercial nylon needle filter to a syringe, which was applied for extracting 1-hydroxypyrene from a urine sample via hydrophobic and hydrogen bond interactions. The nylon membrane in the needle filter acted as the solid-phase extraction adsorbent, meanwhile, it filtered the particles in the urine sample. To obtain high extraction efficiency, key parameters influencing extraction recovery were investigated. The entire pretreatment process was accomplished within 5 min under the optimal conditions. By coupling high-performance liquid chromatography–ultraviolet, a rapid, low-cost, and convenient nylon needle filter-based method was established for the analysis of 1-hydroxypyrene in a complex urine matrix. Within the linearity range of 0.2–1000 μg/L, the method exhibited a satisfactory correlation coefficient (R = 0.9999). The limit of detection was 0.06 μg/L, and the recoveries from urine sample spiked with three concentrations (5, 20, and 100 μg/L) ranged from 105.8% to 113.1% with the relative standard deviations less than 6.7% (intra-day, n = 6) and 8.9% (inter-day, n = 4). Finally, the proposed method was successfully applied for detecting 1-hydroxypyrene in urine samples from college students, smokers, gas station workers, and chip factory workers. The detected concentration in actual urine samples ranged from 0.46 to 5.26 μg/L. Taken together, this simple and cost-effective nylon needle filter-based solid-phase extraction device showed an excellent application potential for pretreating hydrophobic analytes from aqueous samples.     

Quantification of eight active ingredients in crude and processed radix polygoni multiflori applying miniaturized matrix solid‐phase dispersion microextraction followed by UHPLC

A rapid, efficient, and green sample preparation method has been developed to extract eight active ingredients (gallic acid, catechins, epicatechin, polydatin, 2,3,5,4′‐tetrahydroxystilbene‐2‐O‐β‐d ‐glucoside, resveratrol, emodin, and physcion) in radix polygoni multiflori by miniaturized matrix solid‐phase dispersion microextraction. Simple and sensitive ultra high performance liquid chromatography combined with ultraviolet detection has been applied to analyze the multiple compounds. The best results were obtained by adding 25 mg sample into 25 mg adsorbent and grinding for 2 min with disorganized silica as adsorbent and 1 mL 150 mM 1‐dodecyl‐3‐methylimidazolium bromide as a green eluting solvent. Good linearity (r² > 0.998) for each analyte was obtained by this method. The intra‐day and inter‐day precision (RSD) were both below 5.31%, and the recoveries of the analytes ranged from 93.3 to 100.0%. This simple miniaturized matrix solid‐phase dispersion microextraction method for analyzing the compounds in radix polygoni multiflori needs a short time and requires little sample and reagent. Thus, this method is far more eco‐friendly and efficient than traditional extraction methods (reflux and ultrasound‐assisted extraction). The present investigation provided a promising method for the fast preparation and discrimination of chemical differences in crude and processed radix polygoni multiflori.     

GC�CMS Determination of PAHs in Fish Samples Following Salting-out-Assisted Solvent Extraction-Gel Permeation Chromatography

A fast and effective sample cleanup procedure for the quantification of polycyclic aromatic hydrocarbons (PAHs) in fish samples is presented. The procedure involved extraction of fish samples using acetonitrile and cleanup by an automated gel-permeation chromatography (GPC) following liquid?Cliquid partition into n-hexane. The extracted samples were analyzed by gas chromatography-mass spectrometry (GC?CMS). Electron ionization was employed in a single analysis for the determination of PAHs in the selected ion monitoring mode. Three different solvents were studied for the extraction step: acetonitrile/n-hexane, methanol/n-hexane and acetone/n-hexane. The best solvent was found to be acetonitrile/n-hexane. The cleanup technique resulted in a good separation of analytes from co-extractive matrix compounds.     

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.     

Peroxyoxalate chemiluminescence detection for the highly sensitive determination of fluorescence-labeled chlorpheniramine with Suzuki coupling reaction

A sensitive and selective high performance liquid chromatography-peroxyoxalate chemiluminescence (PO-CL) method has been developed for the simultaneous determination of chlorpheniramine (CPA) and monodesmethyl chlorpheniramine (MDCPA) in human serum. The method combines fluorescent labeling with 4-(4,5-diphenyl-1H-imidazole-2-yl)phenyl boronic acid using Suzuki coupling reaction with PO-CL detection. CPA and MDCPA were extracted from human serum by liquid–liquid extraction with n-hexane. Excess labeling reagent, which interfered with trace level determination of analytes, was removed by solid-phase extraction using a C18 cartridge. Separation of derivatives of both analytes was achieved isocratically on a silica column with a mixture of acetonitrile and 60 mM imidazole-HNO₃ buffer (pH 7.2; 85:15, v/v) containing 0.015% triethylamine. The proposed method exhibited a good linearity with a correlation coefficient of 0.999 for CPA and MDCPA within the concentration range of 0.5–100 ng/mL. The limits of detection (S/N = 3) were 0.14 and 0.16 ng/mL for CPA and MDCPA, respectively. Using the proposed method, CPA could be selectively determined in human serum after oral administration.     

Phytic acid induced three‐dimensional graphene for the enrichment of phthalate esters from bottled water and sports beverage samples

A three‐dimensional graphene was synthesized through a hydrothermal reaction of graphene oxide with phytic acid. The microstructure and morphology of the phytic acid induced three‐dimensional graphene were investigated by nitrogen adsorption–desorption isotherms, scanning electron microscopy, and transmission electron microscopy. With a large surface area and three‐dimensional structure, the graphene was used as the solid‐phase extraction adsorbent for the extraction of phthalate esters from bottled water and sports beverage samples before high‐performance liquid chromatographic analysis. The results indicated that the graphene was efficient for the solid‐phase extraction of phthalate esters. The limits of detection (S/N = 3) of the method for the analytes were 0.02–0.03 ng/mL for the water samples and 0.03–0.15 ng/mL for the sports beverage sample. The limits of quantitation (S/N = 9) for the analytes were 0.06–0.09 ng/mL for water samples and 0.09–0.45 ng/mL for sports beverage sample. The calibration curves for the phthalate esters by the method had a good linearity from 0.1 to 80.0 ng/mL with correlation coefficients larger than 0.9997. The recoveries of the analytes for the method fell in the range of 86.7–116.2% with the relative standard deviations between 1.5 and 6.8%.     

Preparation of hydrophilic molecularly imprinted solid‐phase microextraction fiber for the selective removal and extraction of trace tetracyclines residues in animal derived foods

The present work reported a novel hydrophilic and selective solid‐phase microextraction fiber by improved multiple co‐polymerization method immobilization of tetracycline molecularly imprinted polymer on a stainless steel wire and directly coupled with high‐performance liquid chromatography for sensitive determination of trace tetracyclines residues in animal derived foods. The developed molecularly imprinted polymer coated solid‐phase microextraction fibers were characterized through scanning electron microscopy, Fourier transfer infrared spectroscopy, thermogravimetric analysis, and adsorption experiments, the fiber with cross‐linked and porous structure was observed and high thermal and chemical stability. The maximum adsorption capacity of this fiber with good selectivity reached 2.35 µg/mg in aqueous matrices, and showed good repeatability (relative standard deviation ≤ 6.6%, n = 5) and satisfying reproducibility between fiber to fiber (relative standard deviation ≤ 7.8%, n = 5). Under the optimized solid‐phase microextraction conditions, satisfactory linearity (5–1000 µg/L) and detection limits (0.38–0.72 µg/kg, S/N = 3) for all the tetracyclines were obtained. The practicality of this method was proved by adding tetracycline, oxytetracycline at three levels to milk, chicken, and fish samples with good recoveries of 77.3–104.4%.     

液液提取-固相萃取-高效液相色谱-串联质谱测定人体血液中16种有机磷酸酯

人体体液中有机磷酸酯(OPEs)浓度的测定对于了解人体OPEs的暴露水平以及评估人体健康风险具有重要意义.然而,目前的研究大多数集中于尿液中OPEs代谢物含量的分析测定,将其作为人体OPEs暴露的生物标志物,而对人体血液中OPEs的分析研究较少,仅有的少量研究涉及的OPEs种类有限.该研究在优化前处理过程(固相萃取,S...     

Ultrasound‐assisted extraction and solid‐phase extraction for the simultaneous determination of five amide herbicides in fish samples by gas chromatography with electron capture detection

An efficient sample extraction and clean‐up method was developed for simultaneous determination of five amide herbicides (alachlor, acetochlor, propisochlor, metazachlor, and butachlor) in fish samples. The protocol consisted of ultrasound‐assisted solvent extraction and solid‐phase extraction clean‐up. In detail, aliquots of homogenized fish flesh were thoroughly mixed with 20 mL of n‐hexane and then extracted with ultrasonication for 40 min. Each sample was centrifuged and the supernatant was collected for the subsequent clean‐up. For the sample preparation, the above supernatant was processed with a C₁₈ column with 3 mL of dichloromethane/n‐hexane (1:1, v/v) as the eluant. Then the samples were analyzed by gas chromatography with electron capture detection. The correlation coefficients of the five calibration curves were 0.9976–0.9998 (n = 3). The limits of detection (S/N = 3, n = 11) and limits of quantification (S/N = 10, n = 11) were 0.19–0.42 and 0.63–1.39 μg/kg, respectively. The recoveries of this method were 71.2–92.6% with good precision (<4.7% relative standard deviations, n = 6). The developed method was successfully applied to monitor the five amide herbicides in fish samples collected from different cities.     

Dispersive magnetic solid‐phase extraction of phthalate esters from water samples and human plasma based on a nanosorbent composed of MIL‐101(Cr) metal–organic framework and magnetite nanoparticles before their determination by GC–MS

In this study, a magnetic metal–organic framework was synthesized simply and utilized in the dispersive magnetic solid‐phase extraction of five phthalate esters followed by their determination by gas chromatography with mass spectrometry. First, MIL‐101(Cr) was prepared hydrothermally in water medium without using highly corrosive hydrofluoric acid, utilizing an autoclave oven heat supply. Afterward, Fe₃O₄ nanoparticles were decorated into the matrix of MIL‐101(Cr) to fabricate magnetic MIL‐101 nanocomposite. The nanocomposite was characterized by various techniques. The parameters affecting dispersive magnetic solid‐phase extraction efficiency were optimized and obtained as: a sorbent amount of 15 mg; a sorption time of 20 min; an elution time of 5 min; NaCl concentration, 10% w/v; type and volume of the eluent 1 mL n‐hexane/acetone (1:1 v/v). Under the optimum conditions detection limits and linear dynamic ranges were achieved in the range of 0.08–0.15 and 0.5–200 μg/L, respectively. The intra‐ and interday RSD% values were obtained in the range of 2.5–9.5 and 4.6–10.4, respectively. Ultimately, the applicability of the method was successfully confirmed by the extraction and determination of the model analytes in water samples, and human plasma in the range of microgram per liter and satisfactory results were obtained.     

Solid acids assisted matrix solid‐phase dispersion microextraction of alkaloids by capillary electrophoresis coupled with quadrupole time‐of‐flight mass spectrometry

The quantification of three alkaloids is important because quantitative study is a means of assessing the reliability of the experimental method, and three alkaloids of peimine, peiminine, and peimisine are main active ingredients in Chinese Pharmacopoeia 2015. An effective method based on the matrix solid‐phase dispersion microextraction was developed for the extraction of alkaloid compounds in Fritillariae Thunbergii Bulbus. Target analytes were analyzed by capillary electrophoresis coupled with quadrupole time‐of‐flight mass spectrometry. The optimized experimental condition was that 50 mg Fritillariae Thunbergii Bulbus was blended homogeneously with 10 mg citric acid for 5 min. Two hundred microliters of water acidized by 1 mol/L hydrochloric acid (pH = 4.5) was selected to elute tested alkaloids. The results demonstrated that the investigated method had low limits of detection (1.32–1.59 ng/mL), good recoveries (86.63–98.12%), and reproducibility (relative standard deviations of peak areas < 0.87%). The proposed matrix solid‐phase dispersion microextraction coupled with capillary electrophoresis combined with quadrupole time‐of‐flight mass spectrometry was successfully applied for the extraction of alkaloids in plants.     

Microwave-assisted headspace solid-phase microextraction for the rapid determination of organophosphate esters in aqueous samples by gas chromatography-mass spectrometry

The rapid and solvent-free determination of organophosphate esters (OPEs) in aqueous samples via one-step microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) analysis is described. Tri-n-butyl phosphate (TnBP) and tris-(2-ethylhexyl) phosphate (TEHP) were selected as model compounds for the method of development and validation. The effects of various extraction parameters for the quantitative extraction of these analytes by MA-HS-SPME were systematically investigated and optimized. The analytes, in a 20 mL water sample (in a 40 mL sample bottle containing 2 g of NaCl, pH 3.0), were efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 140 W for 5 min. The limits of quantification (LOQs) for TnBP and TEHP were 0.5 and 4 ng/L, respectively. Using the standard addition method, MA-HS-SPME coupled with GC-MS was utilized to determine selected OPEs in surface water and wastewater treatment plants (WWTP) influent/effluent samples. Preliminary results show that TnBP was commonly detected OPEs in these aqueous samples, the correlation coefficients (r²) of the standard addition curves were greater than 0.9822, indicating that the developed method appears to be a good alternative technique for analyzing OPEs in aqueous samples.